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CHEMISTRY FAST TRACK

REVISION MODULE

GRADE XII
2022-23

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SOLUTIONS

ELECTROCHEMISTRY

CHEMICAL KINETICS

D AND F BLOCK

COORDINATION CHEMISTRY

HALOALKANES AND HALOARENES

ALCOHOLS, PHENOLS AND

ETHERS

ALDEHYDES, KETONES AND

CARBOXYLIC ACID

ORGANIC CHEMISTRY CONTAINING

NITROGEN

BIOMOLECULES

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CHAPTER
SOLUTIONS
2
Solutions are homogeneous mixtures of two or more than two components. By homogenous mixture we
mean that its composition and properties are uniform throughout the mixture. Generally, the component
that is present in the largest quantity is known as solvent. Solvent determines the physical state in which
solution exists. Other component present in the solution other than solvent are called solutes.

➢ EXPRESSING CONCENTRATION OF SOLUTIONS

The concentration of a solution may be defined as the amount of solute present in the given quantity of
solvent.

1. Mass Percent (M/M) : It’s defined as the amount of solute in grams present in 100 grams of solution

Mass Percentage of solute = Mass of solute x100

Massof solution

2. Volume Percent (V/V): It’s defined as the volume of the solute in mL present in 100 mL solution.

Volume Percent = Volume of solute x100

Volume of solution

3. Mass percent by volume : It’s defined as mass of solute present 100 mL of solution

Mass of solute
Percent of solute mass by volume = x100
Vol. of solution

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4. Normality : It’s defined as number of gram equivalents of solute present per litre of solution

Number of grame equivalents

Normality =
Volume of solution in litres

Given Mass
Where, No. of grams equivalents = Equivalent mass

Molar mass
And equivalent Mass =
n factor

5. Parts per million : When a solute is present in trace quantities, it is convenient to express concentration
in parts per million (ppm) and is defined as:

6. Mole fraction: Commonly used symbol for mole fraction is x and subscript used on the right hand side
of x denotes the component. It is defined as:

7. Molarity: Molarity (M) is defined as number of moles of solute dissolved in one litre of solution.

8. Molality : Molality (m) is defined as the number of moles of the solute per kilogram (kg) of the solvent
and is expressed as:

Molality is independent of temperature (as coefficient of expansion in liquids is negligible as compared to

the solids) so, molarity is a function of temperature. This is because molality is preferred.

➢ SOME IMPORTANT RELATIONSHIP: -

I. m (Molality) and M (Molarity)

1000 M
m=
1000 d − m A M

Where d = density and mA = Molar Mass of solute

II. M (Molarity) and N (Normality)

N=nxM

Where n means: -

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For Acids: - no. of replaceable H+

For Bases: - no. of replaceable OH-
For salts: - Positive or negative charge
For oxidizing and reducing agents: n means change in oxidising number of oxidising or reducing agent

III. Molarity on mixing: -

M1V1 = M2V2
Where M1 & V1 are the molarity and volume before mixing and M2 & V2 shows values after Mixing

IV. X (mole fraction) and m (molality)

1000 X
m= A
(1 − X ) m B
A

Where XA means mole fraction of solute and mB = Molar of solvent.

➢ SOLUBILITY OF SOLID IN LIQUID

Solubility of solids m liquids basically depends on two factors: -

(a) Lattice enthalpy – The amount of heat required to break 1 mole of a crystal lattice into its free ions
or atoms. It’s here on endothermic phenomena.

(b) Hydration enthalpy: - The Amount of heat liberated when 1 mole of free atoms or ion gets
completely wet by the solvent molecules. It’s here an exothermic phenomenon.

Thus, the solubility of solid in liquid takes place only if the energy released during hydration enthalpy can
compensate lattice enthalpy.

Ex – Salt dissolute in water as its hydration enthalpy is greater than its lattice enthalpy while chalk powder
didn’t dissolute as its lattice enthalpy has higher magnitude than its hydration enthalpy

It is observed that polar solutes dissolve in polar solvents and non-polar solutes in non-polar solvents. In
general, a solute dissolve in a solvent if the intermolecular interactions are similar in the two or we may say
like dissolves like. When a solid solute is added to the solvent, some solute dissolves and its concentration
increases in solution. This process is known as dissolution. Some solute particles in solution collide with
the solid solute particles and get separated out of solution. This process is known as crystallization.

A stage is reached when the two processes (dissolution and crystallization) occur at the same rate. Under
such conditions, number of solute particles going into solution will be equal to the solute particles separating
out and a state of dynamic equilibrium is reached.

At this stage the concentration of solute in solution will remain constant under the given conditions, i.e.,
temperature and pressure, such a solution in which no more solute can be dissolved at the same temperature
and pressure is called a saturated solution. An unsaturated solution is one in which more solute can be
dissolved at the same temperature.

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➢ SOLUBILITY OF GAS IN LIQUID

Gases dissolve in liquid to homogeneous solutions. For example, soda water contains carbon dioxide
dissolved in water under high pressure. The solubility of a gas in liquid is also called as solubility co-
efficient, it can be defined as the volume of the gas in cm3 which will dissolve in 1 cm3 of the liquid to form
a saturated solution at a particular temperature and pressure.

Solubility of a gas in a liquid can be determined by the

• Nature of the gas and the solvent

• Temperature: the solubility of a gas decreases with increase in temperature because on heating the
solution of a gas, some gas is usually expelled out of the solution.

• Pressure: the solubility of a gas in liquid increases with pressure.

Henry’s law gives a quantitative relationship

between the solubility of a gas and the pressure. This
law states that at a given temperature the mass of
dissolved gas in a given volume of solvent is
proportional to the pressure of the gas with which it
is at equilibrium.

The most commonly used form of Henry’s law states

that “the partial pressure of the gas in vapour
phase (p) is proportional to the mole fraction of the
gas (x) in the solution” and is expressed as:

KH = henry constant Different gases have different KH values at the same Temperature. This suggests that
KH is a function of the nature of the gas.

Factors Affecting the Henrys Law Constant

1. The nature of the gas

2. Nature of solvent
3. Temperature
4. The units of pressure

Therefore, different gases have different Henry's laws constant in different solvents, as illustrated
graphically above.

The solubility of a gas in liquid decreases with an increase in Henry's Law constant (KH), at a given
pressure.
This means at a given pressure higher the value of KH (Henry's Law constant), the lower is the solubility of
the gas in a liquid and vice versa.

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Applications of Henry’s law: -

1) To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure.

2) For Scuba divers increased pressure increases the solubility of atmospheric gases in blood. When the
divers come towards surface, the pressure gradually decreases. This releases the dissolved gases and leads
to the formation of bubbles of nitrogen in the blood. This blocks capillaries and creates a medical condition
known as bends, which are painful and dangerous to life. To avoid bends, as well as, the toxic effects of
high concentrations of nitrogen in the blood, the tanks used by scuba divers are filled with air diluted with
helium which is more soluble.

3) At high altitudes the partial pressure of oxygen is less than that at ground level. This leads to the low
solubility of oxygen in blood and because of that climbers becomes weak and makes them unable to think
clearly, symptoms of a condition known as anoxia.

Limitations of Henry’s law:

This law is only valid when the pressure is low, temperature is low, the gas is not highly soluble and the
gas neither reacts chemically with the solvent nor dissociates or associates in the solution in the solvent.

➢ SOLUBILITY OF LIQUID IN LIQUID

Let us consider a binary solution of two volatile liquids and denote the two components as 1 and 2. When
taken in a closed vessel, both the Components would evaporate and eventually equilibrium would be
established between vapour phase and the liquid phase.
Then according to Raoult’s law a solution of volatile liquids, the partial vapour pressure of each
component in the solution is directly proportional to its mole fraction.
Thus, for component 1

According to Dalton’s law of partial pressures, the total pressure ( total p ) over the solution phase in the
container will be the sum of the partial pressures of the components of the solution and is given as:

Raoult’s law as a special case of Henry’s law

In the solution of a liquid in liquid, if one of the components is too volatile that initially it was taken as a
liquid but due to its high volatility it achieves gas form. Thus, at initial we can apply raoult’s law when its
liquid in liquid type but when it exists as gas, we can apply henry’s law.

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p1 = p1ox1 (Raoults law)

p = KH χ (Henry’s law)
so, at this stage KH(henry constant) = p1o(vapour pressure of pure component)

➢ CLASSIFICATION OF LIQUID-LIQUID SOLUTION TYPE

1) Ideal Solutions

The solutions which obey Raoult’s law over the entire range of Concentration are
known as ideal solutions. The ideal solutions have two other important properties.
ΔHmix = 0 and ΔVmix= 0
It means that no heat is absorbed or evolved when the components are mixed.
Also, the volume of solution would be equal to the sum of volumes of the two
components.
If the intermolecular attractive forces between the A-A and B-B are Nearly equal
to those between A-B, this leads to the formation of ideal solution. A perfectly
ideal solution is rare but some solutions are nearly ideal in behavior.

2) Non-ideal Solutions

When a solution does not obey Raoult’s law over the entire range of Concentration, then it is called non-
ideal solution. Non- ideal solutions show two types of deviations from ideality.
Positive deviation if A-B (solute and solvent) interactions are weaker than
those A-A (solute-solute) or B-B (solvent –solvent) then more escaping takes
place which results an increase in vapour pressure than that of ideality.
Example Mixtures of ethanol and acetone behave in this manner. In pure ethanol,
molecules are hydrogen bonded. On adding acetone, its molecules get in between
the host molecules and break some of the hydrogen bonds between them. Due to
weakening of interactions, the solution shows positive deviation from Raoult’s
law

Negative deviations the intermolecular Attractive forces between A-A and B-

B are weaker than those between A-B which means stronger bonding and lesser
escaping and hence vapour pressure decreases than that of ideal gases.
Ex a mixture of chloroform and acetone forms a solution with negative
deviation from Raoult’s law. This is because chloroform molecule is able to
form hydrogen bond with acetone and forms strong bonds

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➢ AZEOTROPES

Some liquids on mixing form azeotropes which are binary constant boiling mixtures having the same
composition in liquid and vapour phase and boil at a constant temperature. In such cases, it is not possible
to separate the components by fractional distillation. The solutions which show a large positive deviation
from Raoult’s law form minimum boiling azeotrope

For example, ethanol-water mixture

The solutions that show large negative deviation from Raoult’s law form maximum boiling azeotrope at a
specific composition.
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For example, Nitric acid and water, these solutions shows large positive deviation from Raoult’s law form
minimum boiling azeotrope at a specific composition.

Maximum Boiling Azeotrope Minimum Boiling Azeotrope

The boiling point of this azeotrope is lower than
the boiling points of its constituents.
This solution exhibits large positive deviation
from Raoult's law and large vapour pressure
difference of components.
Example: Ethanol boils at 78.40C, water boils at
1000C, but the azeotrope boils at 78.20C, which
is lower than either of its constituents.
The boiling point of this azeotrope is higher than the
boiling points of its constituents.
The maximum boiling azeotrope occurs if the solution
exhibits negative deviation from ideality
Example: Hydrogen chloride boils at -840C and water
at 1000C, but the azeotrope boils at 1100C, which is
higher than either of its constituents.

➢ COLLIGATIVE PROPERTIES

All these properties depend on the number of solute particles irrespective of their nature relative to the total
number of particles present in the solution. Such properties are called colligative properties.

1) RELATIVE LOWERING OF VAPOUR PRESSURE

If a non-volatile solute is added to a solvent to give a solution

the vapour pressure of the solution is solely from the solvent
alone. In the solution, the surface has both solute and solvent
molecules; thereby the fraction of the surface covered by the
solvent molecules gets reduced. Consequently, the number of
solvent molecules escaping from the surface is correspondingly
reduced, thus, the vapour pressure is also reduced. The
decrease in the vapour pressure of solvent depends on the
quantity of non-volatile solute present in the solution,
irrespective of its nature (called as colligative properties)

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2) ELEVATION OF BOILING POINT (EBULLIOSCOPY)

Since boiling point is temperature at which the vapour pressure of the

liquid becomes equal to the atmospheric pressure surrounding the liquid
and relative lowering in vapour pressure shows that to re-attain the
equilibrium between liquid and gas phase, boiling point is achieved at
higher temperature. It means that if vapour pressure is decreased then
higher temperature is required to boil it.

ΔTb(Tb - Tb0) = molality × Kb

Where Kb = ebullioscopic constant or molal heat constant which is 0.51°C kg/mol for the boiling point of
water,
ΔTb = Tb - Tb0 (boiling point of solution – boiling point of the pure component)

3) DEPRESSION OF FREEZING POINT (CRYOCSCOPY)

Freezing point of a substance may be defined as the temperature at which the vapour pressure of the
substance in its liquid phase is equal to its vapour pressure in the solid phase.
The lowering of vapour pressure of a solution causes a lowering of the
freezing point compared to that of the pure solvent as lesser vapours means
lesser amount of temperature is required to settle down.

ΔTf (Tf0 – Tf )= molality × Kf

Kf = cryoscopic constant, molal freezing depression constant which is -
1.86°C kg/mol for the freezing point of water.
ΔTf = Tf0 – Tf (freezing point of pure component – freezing point solution)

Significance of Kf:

The molal freezing point depression constant is equal to the depression in the freezing point produced
when one mole of solute is dissolved in 1 kg of the solvent.
Kb and Kf can be obtained from the following relationships:

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NOTE: Camphor is commonly used in determining the molecular mass of a solute because of its very high
cryoscopic constant

4) OSMOSIS AND OSMOTIC PRESSURE

Assume that only solvent molecules can pass through semi permeable membranes. If this membrane is
placed between the solvent and solution the solvent molecules will flow through the membrane from pure
solvent to the solution. This process of flow of the solvent is called osmosis. The flow will continue till
the equilibrium is attained. The flow of the Solvent from its side to solution side across a semi permeable
membrane can be stopped if some extra pressure is applied on the solution. This Pressure that just stops
the flow of solvent is called osmotic pressure of the solution.
The osmotic pressure of a solution is the excess pressure that must be applied to a solution to prevent
osmosis, i.e., to stop the passage of solvent molecules through a semi permeable membrane into the solution.
The flow of solvent from dilute solution to the concentrated solution across a semi permeable membrane is
due to Osmosis. The important point to be kept in mind is that solvent molecules always flow from lower
concentration to higher concentration of solution. The osmotic pressure has been found to depend on the
concentration of the solution.
πV = nRT
(Where: π = osmotic pressure; V is the volume; T is absolute temperature; n is the number of moles of
solute; R = the molar gas constant)
Two solutions having same osmotic pressure at a given temperature are called isotonic solutions. If the salt
concentration is less than the solution it’s said to be hypotonic. If the salt concentration is more than the
solution then it’s said to be hypertonic.

Osmotic pressure has advantages for finding out the molar mass over other collegative properties as
pressure measurement is around room temperature and molarity is used instead of molality . As compared
to the other collegative properties osmotic pressure's magnitude is large enough even for the dilute
solution.

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➢ BIOLOGICAL IMPORTANCE OF OSMOSIS

Plants absorb water from the soil through their roots due to osmosis, people taking a lot of salt or salty food
experience water retention in tissue cells and intercellular spaces because of osmosis. The resulting
puffiness or swelling is called edema. Moreover, the use of salt and sugar as preservatives in pickles and
jams has its basis in preventing the growth of fungi and bacteria by osmosis.

➢ REVERSE OSMOSIS AND WATER PURIFICATION

The direction of osmosis can be reversed if a pressure larger than the osmotic
pressure is applied to the solution side. That is, now the pure solvent flows out
of the solution through the semi permeable membrane. This phenomenon is
called reverse osmosis and is of great practical utility. Reverse osmosis is used
in desalination of sea Water. When pressure more than osmotic pressure is
applied, pure water is squeezed out of the sea Water through the membrane.

Osmosis Diffusion
It Is limited only to the liquid medium. Occurs In all mediums - Solid, Liquid and gas.
Requires a semipermeable membrane. Do not require a semipermeable membrane.
Only the solvent molecules can diffuse. Both the molecules of solute and solvent can diffuse.

The flow of particles occurs only in one direction. The flow of particles occurs in all the directions.

➢ Some examples of Osmosis in everyday life are: -

1. when you keep raisin in water and the raisin gets puffed.
2. Movement of salt-water in animal cell across our cell membrane.
3. Plants take water and mineral from roots with the help of Osmosis.
4. If you are there in a bath tub or in water for long your finger gets pruned. Finger skin absorbs water
and gets expanded.
5. It is used for preservation of fruits and meat.

➢ Semi permeable Membrane

The semipermeable membranes allow a selective passage to only the solvent molecules. Cellophane,
parchment paper and animal protein membranes are typical semipermeable membranes.

o The most frequently used semipermeable membrane in the laboratory is that of copper ferrocyanide,
Cu2[Fe(CN)6] because it is very strong and can withstand very high pressure.
o Remember that the semipermeable membrane of Cu2[Fe(CN)6] does not work in non-aqueous
solution because it gets dissolved in nonaqueous solvents. Another synthetic semipermeable
membrane is that of calcium phosphate.

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o Natural semipermeable membranes are cell walls, pig's bladder, the skin surrounding white of an egg,
the membrane surrounding RBCs etc.

➢ Van't Hoff factor and degree of dissociation:

The fraction of the total number of molecules which dissociates in the solution into simple ions or
molecules is
called the degree of dissociation.
Ex. NaCl Na+ + Cl– (i = 2)
Ex. K2SO4 2K+ + SO42– (i = 3)
Ex. for complex compound
K4[Fe(CN)6] 4K+ + [Fe(CN)6]4– (n = 5)

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SECTION 1: CONCENTRATION OF SOLUTIONS AND SOLUBILITY

1. What is the molarity of H2SO4 solution which has a density 1.84 g/cc at 350C and contains 98% by
weight? (18.4 M)
2. Calculate: a) molality b) molarity c) mole fraction of Kl if the density of 20 % (mass\mass) aqueous
Kl is 1.202 g mol-1
3. If the molality of an aqueous solution of cane sugar is 0.4445, what is the mole fraction of cane
sugar? (0.0079)
4. A sample of drinking water was found to be severely contaminated with chloroform (CHCl3),
supposed to be carcinogen. The level of contamination was 15 ppm (by mass0.
Express this in per cent by mass.
Determine the molality of chloroform in the water sample. (1.25 x 10-4m)
5. The partial pressure of ethane over a saturated solution containing 6.56 x 10-3 g of ethane is 1 bar.
If the solution contains 5.00 x 10-2g of ethane, then what shall be the partial pressure of the gas?
(7.62 bar)
6. Nalorphene (C19H21NO3), similar to morphine, is used to combat withdrawal symptoms in narcotic
users. Does of nalorphrnr generally given is 1.5 mg. Calculate the mass of 1.5 x 10-3 m aqueous
solution required for the above dose. (3.21 g)
7. The air is a mixture of a number of gases. The major components are oxygen and nitrogen with
approximate proportion of 20% is to 79% by volume at 298 K, respectively. The water is in
equilibrium with air at a pressure of 10 atm. At 298 K, if the Henry’s law constant for oxygen and
nitrogen are 3.30 x 107 mm and 6.51 x 107 mm respectively, calculate the composition of these gases
in water. (9.22 x 10-5)
8. An antifreeze solution is prepared from 222.6 g of ethylene glycol (C2H6O2) and 200 g of water.
Calculate the molality of the solution. If the density of the solution is 1.2 g mL-1, then what shall be
the molarity of the solution? (0.67 M)
9. Suggest the most important type of intermolecular interaction in the following pairs:
i. n- hexane and n-octane
ii. I2 and CCl4
iii. NaClO4 and water
iv. Methanol and acetone
v. Acetonitrile (CH3CN) and acetone (C3H6O)
vi. Water and alcohol
10. Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250 mL of 0.15 M
solution in methanol. (4.575 g)
11. How many mL of a 0.1 M HCl are required to react completely with 1 g mixture of Na2CO3 and
NaHCO3 containing equimolar amounts of both? ( 157.2 mL)
SECTION 2: VAPOUR PRESSURE OF LIQUID SOLUTIONS

Very Short Answer Questions

1. A and B liquids on mixing produce a warm solution. Which type of deviation from Raoult’s law is
there?

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2. Two liquids A and B boil at 1550C and 1900C, respectively. Which of them has a higher vapour
pressure at 800C?
Short Answers Questions

1. What type of deviation is shown by a mixture of ethanol and acetone? Give reason.
2. H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of
H2S in water at STP is 0.195 m, calculate Henry’s law constant.
3. Henry’s law constant for CO2 in water is 1.67 × 108 Pa at 298 K. Calculate the quantity of CO2 in
500 mL of soda water when packed under 2.5 atm CO2 pressure at 298 K.
4. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively at 350. Find out
the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find the
composition of the vapour phase.
5. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea (NH2CONH2) is dissolved in
850 g of water. Calculate the vapour pressure of water for this solution and its relative lowering.
6. When water and nitric acid are mixed together, a rise in temperature is observed. What type of
azeotropic mixture is obtained?
7. The vapour pressures of pure liquids A and B are 450 and 700 mm Hg at 350 K, respectively. Find
composition of the liquid mixture, if total vapour pressure is 600 mm Hg. Also, find the composition
of the vapour phase. (0.70)
8. Why is vapour pressure of a solution of glucose in water lower than that of water?
9. Heptane and octane form ideal solution. At 373 K, the vapour pressures of the two liquid
components are 105.2 kPa and 46.8 kPa, respectively. What will be the vapour pressure of a mixture
of 26.0 g of heptane and 35.0 g of octane? (73.43 kPa)
10. Benzene and toluene form ideal solution over the entire range of composition. The vapour pressures
of pure benzene and toluene at 300 K are 50.71 mm Hg and 32.06mm Hg, respectively. Calculate
the mole fraction of benzene in the vapour phase, if 80g of benzene is mixed with 100 g of toluene.
(0.6)
11. At 250C the vapour pressures of benzene (C6H6) and toluene (C7H8) are 93.4 torr and 26.9 torr,
respectively. A solution is made by mixing 35.0 g of benzene and 65.0g of toluene. At what applied
pressure, in torr, will this solution boil at 250C? (52.7 torr)
SECTION 3: COLLIGATIVE PROPERTIES AND MISCELLANEOUS

Very Short Answers Questions

1. What is de-icing agent? How does it function?

2. It is advised to add ethylene glycol to water in car radiator while driving in hill station. Why?
3. At higher altitudes, people suffer from a disease called anoxia. In this disease, they become weak
and cannot think clearly?
4. Scuba divers when dives too deep they suffer from a medical injury, bends?
5. Why aquatic organisms do are more comfortable in colder water than in warm water?
6. How does sprinkling of water helps in the clearing of the snow?

Short Answer Questions

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1. Why do doctor’s advice gargles by saline water in case of sore throat?

2. Boiling point of water at 750 mm Hg is 99.630 C. How much sucrose is to be added to 500 g of
water such that it boils at 1000 C.?
3. Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75 g of acetic acid to
lower its melting point by 1.50 C. Kf = 3.9 K kg mol-1.
4. Calculate the osmotic pressure in Pascal’s exerted by a solution prepared by dissolving 1.0 g of
polymer of molar mass 185,000 in 450 mL of water at 370 C.
5. A solution of glucose in water is labelled as 10 % w\w, what would be the molarity and the mole
fraction of each component in the solution? If the density of the solution is 1.2 g mL-1, then what
shall be the molarity of the solution?
6. How many mL of 0.1 M HCl are required to react completely with 1 g mixture of Na2CO3 and
NaHCO3 containing equimolar amounts of both?
7. An antifreeze solution is prepared from 222.6 g of ethylene glycol, (C2H6O2), and 200 g of water.
Calculate the molality of the solution. If the density of the solution is 1.072 g mL-1, then what shall
be the molarity of the solution?
8. An aqueous solution of 2%, non- volatile solute exerts a pressure of 1.004 bar at the normal boiling
point of the solvent. What is the molar mass of the solute?
9. Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid
components are 105.2 kPa and 46.8 kPa, respectively. What will be the vapour pressure of a mixture
of 26.0 g of heptane and 35 g of octane?
10. The vapour pressure of water is 12.3 kPa at 300 K. Calculate the vapour pressure of 1 molal solution
of a non- volatile solute in it.
11. Calculate the mass of a non- volatile solute (molar mass 40 g mol-1) which should be dissolved in
114 g octane to reduce its vapour pressure to 80%.
12. A solution containing 30g of non- volatile solute exactly in 90 g of water has a vapour pressure of
2.8 kPa at 298 K. Further, 18 g of water is then added to the solution and the new vapour pressure
becomes 2.9 kPa at 298 K. Calculate
a) Molar mass of the solution b) vapour pressure of water at 298 K.
13. A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. calculate the freezing
point of a 5% glucose in water if freezing point of pure water is 273.15 K.
14. Two elements of glucose A and B form compounds having formula AB2 and AB4. When dissolved
in 20 g benzene (C6H6),1 g of AB2 lower the freezing point by 2.3 K whereas 1.0 g of AB4 lowers
it by 1.3 K. The molar depression constant for benzene is 5.1 K kg mol-1. Calculate atomic masses
of A and B.
15. At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure of 4.98 bar. If the
osmotic pressure of the solution is 1.52 bars at the same temperature, what would be its
concentration?
16. Calculate the depression in the freezing point of water when 10 g of CH3CH2CHClCOOH is added
to 250 g of water. Ka = 1.4 × 10-3,Kf = 1.86 K kg mol-1.
17. Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure of water at 293
K when 25 g of glucose is dissolved in 450 g of water.
18. An aqueous solution of sodium chloride freezes below 273 K. Explain the lowering in freezing point
of water with the help of a suitable diagram.

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19. 18 g glucose C6H12O6 (molar mass = 180 g mol-1) is dissolved in 1 kg of water in a sauce pan. At
what temperature will this solution boil? (373.20 K approx.)
(Kb for water = 0.52 kg mol-1, boiling point of pure water = 373.15 K)
20. Calculate the mass of compound (molar mass = 256 g mol-1) to be dissolved in 75 g of benzene to
lower its freezing point by 0.48 K. (Kf = 5.12K kg mol-1)
21. At 250C, the saturated vapour pressure of water is 3.165 kPa (23.75 mm Hg). Find the saturated
vapour pressure of a 5% aqueous solution of urea (carbamide) at the same temperature. (Molar mass
of urea = 60.05 g mol-1). (3.115 kPa)
22. 15.0 g of unknown molecular material is dissolved in 450 g of water. The resulting solution freezes
at -0.340C. What is the molar mass of the material? (K f for water = 1.86 K kg mol-1). (182.35 g
mol-1)
23. A solution containing 15 g urea (molar mass = 60 g mol-1) per litre of solution in water has the same
osmotic pressure (isotonic) as a solution of glucose (molar mass = 180 g mol-1) in water. Calculate
the mass of glucose present in one litre of its solution. (45 g)
24. Calculate the boiling point of one molar aqueous solution. Density of KBr solution is 1.06 g mL-1,
(Kb for H2O= 0.52 K kg mol-1, atomic mass, K = 38, Br = 80). ( 373.553 K)
25. What will be the osmotic pressure of α 0.1 M monobasic acid, if its pH is 2.0 at 250C. (2.69 atm)
26. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea (NH2CONH2) is dissolved in
850 g of water. Calculate the vapour pressure of water for this solution and its relative lowering. (
0.018)
27. Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75 g of acetic acid to
lower its melting point by 1.50C. (Kf = 3.9 K kg mol-1).(5.077 g)
28. A solution of urea in water has a boiling point of 373.128 K. Calculate the freezing point of the
same solution. (Given, for water Kf = 1.85 km-1 and Kb = 0.52 km-1). (0.458 K)
29. Boiling point of water at 750 mm Hg is 99.630C. How much sucrose is to be added to 500 g of water
such that is boils at 1000C? Molar elevation constant for water is 0.52 K kg mol-1. ( 121.67 g)
30. A solution of 3.800 g of sulphur in 100 g of CS2 (B.P = 246.30oC) boils at46.66oC. What is the
formula of sulphur molecule in this solution?

➢ EXEMPLAR QUESTIONS

1. Which of the following units is useful in relating
concentration of solution with its vapour
pressure?
(i) mole fraction
(ii) parts per million
(iii) mass percentage
(iv) molality
2. On dissolving sugar in water at room
temperature solution feels cool to touch.
Under which of the following cases dissolution
of sugar will be most rapid?
(i) Sugar crystals in cold water.
(ii) Sugar crystals in hot water.
(iii) Powdered sugar in cold water.
(iv) Powdered sugar in hot water.
3. At equilibrium the rate of dissolution of a solid
solute in a volatile liquid solvent is _________
(i) less than the rate of crystallisation
(ii) greater than the rate of crystallisation

18
 JMD ੴ
(iii) equal to the rate of crystallisation
(iv) zero
4. A beaker contains a solution of substance ‘A’.
Precipitation of substance ‘A’ takes place when
small amount of ‘A’ is added to the solution. The
solution is _____________.
(i) saturated
(ii) supersaturated
(iii) unsaturated
(iv) concentrated
5. Maximum amount of a solid solute that can be
dissolved in a specified amount of a given liquid
solvent does not depend upon
(i) Temperature
(ii) Nature of solute
(iii) Pressure
(iv) Nature of solvent
6. Low concentration of oxygen in the blood and
tissues of people living at high altitude is due to
(i) low temperature
(ii) low atmospheric pressure
(iii) high atmospheric pressure
(iv) both low temperature and high atmospheric
pressure
7. Considering the formation, breaking and strength
of hydrogen bond, predict which of the following
mixtures will show a positive deviation from
Raoult’s law?
(i) Methanol and acetone.
(ii) Chloroform and acetone.
(iii) Nitric acid and water.
(iv) Phenol and aniline.
8. Colligative properties depend on.
(i) the nature of the solute particles dissolved in
solution.
(ii) the number of solute particles in solution.
(iii) the physical properties of the solute particles
dissolved in solution.
(iv) the nature of solvent particles.
9. Which of the following aqueous solutions should
have the highest boiling point?
(i) 1.0 M NaOH
(ii) 1.0 M Na2SO4
(iii) 1.0 M NH4NO3
(iv) 1.0 M KNO3
10. The unit of ebulioscopic constant is
(i) K kg mol–1 or K (molality)–1
(ii) mol kg K–1 or K–1(molality)
(iii) kg mol–1 K–1 or K–1(molality)–1
(iv) K mol kg–1 or K (molality)
11. In comparison to a 0.01 M solution of glucose,
the depression in freezing point of a 0.01 M
MgCl2 solution is
(i) the same
(ii) about twice
(iii) about three times
(iv) about six times
12. An unripe mango placed in a concentrated salt
solution to prepare pickle, shrivels because .
(i) it gains water due to osmosis.
(ii) it loses water due to reverse osmosis.
(iii) it gains water due to reverse osmosis.
(iv) it loses water due to osmosis.
13. At a given temperature, osmotic pressure of a
concentrated solution of a substance .
(i) is higher than that at a dilute solution.
(ii) is lower than that of a dilute solution.
(iii) is same as that of a dilute solution.
(iv) cannot be compared with osmotic pressure
of dilute solution.
14. Which of the following statements is false?
(i) Two different solutions of sucrose of same
molality prepared in different solvents will have
the same depression in freezing point.
(ii) The osmotic pressure of a solution is given
by the equation Π = CRT ( where C is the
molarity of the solution).
(iii) Decreasing order of osmotic pressure for
0.01 M aqueous solutions of barium chloride,
potassium chloride, acetic acid and sucrose is
BaCl2 > KCl > CH3COOH > sucrose.
(iv) According to Raoult’s law, the vapour
pressure exerted by a volatile component of a
19
 JMD ੴ
solution is directly proportional to its mole
fraction in the solution.
15. The values of Van’t Hoff factors for KCl, NaCl
and K2 SO4 , respectively, are
(i) 2, 2 and 2
(ii) 2, 2 and 3
(iii) 1, 1 and 2
(iv) 1, 1 and 1
16. Which of the following statements is false?
(i) Units of atmospheric pressure and osmotic
pressure are the same.
(ii) In reverse osmosis, solvent molecules move
through a semipermeable membrane from a
region of lower concentration of solute to a
region of higher concentration.
(iii) The value of molal depression constant
depends on nature of solvent.
(iv) Relative lowering of vapour pressure, is a
dimensionless quantity.
17. Value of Henry’s constant KH.
(i) increases with increase in temperature.
(ii) decreases with increase in temperature.
(iii) remains constant.
(iv) first increases then decreases.
18. The value of Henry’s constant KH is _______.
(i) greater for gases with higher solubility.
(ii) greater for gases with lower solubility.
(iii) constant for all gases.
(iv) not related to the solubility of gases.
19. Consider the Fig. and mark the correct option.
(i) water will move from side (A) to side (B) if a
pressure lower than osmotic pressure is applied
on piston (B).
(ii) water will move from side (B) to side (A) if a
pressure greater than osmotic pressure is applied
on piston (B).
(iii) water will move from side (B) to side (A) if
a pressure equal to osmotic pressure is applied
on piston (B).
(iv) water will move from side (A) to side (B) if
pressure equal to osmotic pressure is applied on
piston (A).
20. We have three aqueous solutions of NaCl
labelled as ‘A’, ‘B’ and ‘C’ with concentrations
0.1M, 0.01M and 0.001M, respectively. The
value of van’t Hoff factor for these solutions will
be in the order .
(i) iA < iB < iC
(ii) iA > iB > iC
(iii) iA = iB = iC
(iv) iA < iB > iC
21. On the basis of information given below mark
the correct option.
Information:
(A) In bromoethane and chloroethane mixture
intermolecular interactions of A–A and B–B type
are nearly same as A–B type interactions.
(B) In ethanol and acetone mixture A–A or B–B
type intermolecular interactions are stronger than
A–B type interactions.
(C) In chloroform and acetone mixture A–A or
B–B type intermolecular interactions are weaker
than A–B type interactions.
(i) Solution (B) and (C) will follow Raoult’s law.
(ii) Solution (A) will follow Raoult’s law.
(iii) Solution (B) will show negative deviation
from Raoult’s law.
(iv) Solution (C) will show positive deviation
from Raoult’s law.
22. Two beakers of capacity 500 mL were taken.
One of these beakers, labelled as “A”, was filled
with 400 mL water whereas the beaker labelled
“B” was filled with 400 mL of 2 M solution of
NaCl. At the same temperature both the beakers
were placed in closed containers of same
20
 JMD ੴ
material and same capacity as shown in Fig.
At a given temperature, which of the following
statement is correct about the vapour pressure of
pure water and that of NaCl solution.
▪ (i) vapour pressure in container (A) is more than
that in container (B).
▪ (ii) vapour pressure in container (A) is less than
that in container (B).
▪ (iii) vapour pressure is equal in both the
containers.
▪ (iv) vapour pressure in container (B) is twice the
vapour pressure in container (A).
23. If two liquids A and B form minimum boiling
azeotrope at some specific composition then .
(i) A–B interactions are stronger than those
between A–A or B–B.
(ii) vapour pressure of solution increases because
more number of molecules of liquids A and B
can escape from the solution.
(iii) vapour pressure of solution decreases
because less number of molecules of only one of
the liquids escape from the solution.
(iv) A–B interactions are weaker than those
between A–A or B–B.
24. 4L of 0.02 M aqueous solution of NaCl was
diluted by adding one litre of water. The molality
of the resultant solution is .
(i) 0.004
(ii) 0.008
(iii) 0.012
(iv) 0.016
25. 25. On the basis of information given below
mark the correct option.
Information : On adding acetone to methanol
some of the hydrogen bonds between methanol
molecules break.
(i) At specific composition methanol-acetone
mixture will form minimum boiling azeotrope
and will show positive deviation from Raoult’s
law.
(ii) At specific composition methanol-acetone
mixture forms maximum boiling azeotrope and
will show positive deviation from Raoult’s law.
(iii) At specific composition methanol-acetone
mixture will form minimum boiling azeotrope
and will show negative deviation from Raoult’s
law.
(iv) At specific composition methanol-acetone
mixture will form maximum boiling azeotrope
and will show negative deviation from Raoult’s
law.
26. KH value for Ar(g), CO2 (g), HCHO (g) and
CH4 (g) are 40.39, 1.67, 1.83×10–5 and 0.413
respectively.
Arrange these gases in the order of their
increasing solubility.
(i) HCHO < CH4 < CO2 < Ar
(ii) HCHO < CO2 < CH4 < Ar
(iii) Ar < CO2 < CH4 < HCHO
(iv) Ar < CH4 < CO2 < HCHO
Multiple Choice Questions (Type-II)
Note : In the following questions two or more
options may be correct.
27. Which of the following factor (s) affect the
solubility of a gaseous solute in the fixed volume
of liquid solvent?
(a) nature of solute (b) temperature (c) pressure
(i) (a) and (c) at constant T
(ii) (a) and (b) at constant P
(iii) (b) and (c) only
(iv) (c) only
28. Intermolecular forces between two benzene
molecules are nearly of same strength as those
between two toluene molecules. For a mixture of
benzene and toluene, which of the following are
not true?
(i) Δmix H = zero
(ii) Δmix V = zero
21
 JMD ੴ

(iii) These will form minimum boiling azeotrope. 33. In isotonic solutions ________________.
(iv) These will not form ideal solution. (i) solute and solvent both are same.
29. Relative lowering of vapour pressure is a (ii) osmotic pressure is same.
colligative property because __________. (iii) solute and solvent may or may not be same.
(i) It depends on the concentration of a non (iv) solute is always same solvent may be
electrolyte solute in solution and does not different.
depend on the nature of the solute molecules. 34. For a binary ideal liquid solution, the variation in
(ii) It depends on number of particles of total vapour pressure versus composition of
electrolyte solute in solution and does not solution is given by which of the curves?
depend on the nature of the solute particles.
(iii) It depends on the concentration of a non
electrolyte solute in solution as well as on the
nature of the solute molecules.
(iv) It depends on the concentration of an
electrolyte or nonelectrolyte solute in solution as
well as on the nature of solute molecules.
30. Van’t Hoff factor i is given by the expression
_______________.

35. Colligative properties are observed when

___________.
(i) a non volatile solid is dissolved in a volatile
liquid.
(ii) a non volatile liquid is dissolved in another
volatile liquid.
(iii) a gas is dissolved in non volatile liquid.
31. Isotonic solutions must have the same (iv) a volatile liquid is dissolved in another
______________. volatile liquid.
(i) solute
(ii) density Short Answer Type Questions
(iii) elevation in boiling point 36. Components of a binary mixture of two liquids A
(iv) depression in freezing point and B were being separated by distillation. After
32. Which of the following binary mixtures will some time separation of components stopped and
have same composition in liquid and vapour composition of vapour phase became same as
phase? that of liquid phase. Both the components started
(i) Benzene – Toluene coming in the distillate. Explain why this
(ii) Water-Nitric acid happened.
(iii) Water-Ethanol 37. Explain why on addition of 1 mol of NaCl to 1
(iv) n-Hexane – n-Heptane litre of water, the boiling point of water
increases, while addition of 1 mol of methyl

22
 JMD ੴ
alcohol to one litre of water decreases its boiling
point.
38. Explain the solubility rule “like dissolves like” in
terms of intermolecular forces that exist in
solutions.
39. Concentration terms such as mass percentage,
ppm, mole fraction and molality are independent
of temperature, however molarity is a function of
temperature. Explain.
40. hat is the significance of Henry’s Law constant
K?
41. Why are aquatic species more comfortable in
cold water in comparison to warm water?
42. (a) Explain the following phenomena with the
help of Henry’s law.
(i) Painful condition known as bends.
(ii) Feeling of weakness and discomfort in
breathing at high altitude.
(b) Why soda water bottle kept at room
temperature fizzes on opening?
43. Why is the vapour pressure of an aqueous
solution of glucose lower than that of water?
44. How does sprinkling of salt help in clearing the
snow covered roads in hilly areas? Explain the
phenomenon involved in the process.
45. What is “semi permeable membrane”?
46. Give an example of a material used for making
semipermeable membrane for carrying out
reverse osmosis.
47. Assertion : Molarity of a solution in liquid state
changes with temperature.
Reason : The volume of a solution changes with
change in temperature.
48. Assertion : When methyl alcohol is added to
water, boiling point of water increases.
Reason : When a volatile solute is added to a
volatile solvent elevation in boiling point is
observed.
49. Assertion : When NaCl is added to water a
depression in freezing point is observed.
Reason : The lowering of vapour pressure of a
solution causes depression in the freezing point.
50. Assertion : When a solution is separated from
the pure solvent by a semi- permeable
membrane, the solvent molecules pass through
it from pure solvent side to the solution side.
Reason : Diffusion of solvent occurs from a
region of high concentration solution to a region
of low concentration solution.
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 JMD ੴ

CHAPTER

3 ELECTROCHEMISTRY

Electrochemistry is the branch of physical chemistry which deals with the inter-conversion of electrical and
chemical energy.

ELECTROCHEMISTRY

(I) (II) (III)

Electrolytic Cells Electrochemical Cells Characteristics of Cells

➢ PART –I ELECTROLYTICAL CELLS

Works on the principle of electrolysis in which an electric current drives a non – spontaneous reaction
(∆𝐺 = +𝑣𝑒)
ELECTROLYSIS

Qualitative Analysis Quantitative Analysis

This depends on the type of This depends on faradays

electrodes and electrolytes law of electrolysis and
and predicts the end product predicts the amount of gas
of on electrolysis. liberation and mass
depositions at respective
electrodes.

➢ QUALITATIVE ANANLYSIS OF ELECTROLYSIS

The device in which chemical reaction involving redox is carried out with the help of electricity is called
an electrolytic cell. It consist a vessel with two metallic rods which on passing electricity works as electrodes
(electric rods) immersed in an electrolyte whose decomposition is a non-spontaneous reaction.

On passing electricity the electrodes acquires charges, Cation moves towards the – vely charged electrode
i.e. cathode (cation + electrode) to get discharge by gaining electrons from the electrode to undergo
reduction while anion moves toward +ve electrode referred as anode (anion + electrode) and loose electrons
i.e. oxidation for discharging, thus a non- spontaneous reaction becomes spontaneous with the help of
electricity.

24
JMD ੴ

At respective electrodes, there are two types of changes primary and secondary. The conversion of ions into
neutral species at their respective electrodes is called primary change while the product formation from
those neutral species is called secondary change.

Electrolysis largely depends on the nature of the electrodes and electrolytes.

Electrodes can be inert or reactive while electrolytes can be of aqueous or molten and on that basis we can
have the following types of electrolysis.

TYPE I: INERT ELECTRODES AND MOLTEN ELECTROLYTES

Example: Electrolysis of NaCl with platinum electrodes, in which Na+ goes to cathode and Cl- goes to
anode for discharging via reduction and oxidation respectively.

At anode Cl- oxidizes to Cl after the removal of e- which is a primary change but Cl is unstable and not
known thus formation of product i.e. Cl2 takes place which is its secondary change and evolves at anode at
cathode, Na+ gains e- to form metal Na atom liberate at Cathode.

At Anode (oxidation): 2Cl − → Cl 2 + 2e −

At Cathode (reaction): Na + + e − → Na

Over all reaction: 2Cl − + 2 Na + → Cl 2 + 2 Na

( Anode ) ( cathode)

NOTE: Platinum being an inert electrode doesn’t participates in the

reaction and also acts as a good adsorbent for gases.

TYPE II: INERT ELECTRODES AND AQUEOUS ELECTROLYTE

In aqueous electrolyte the ionization of water also takes place apart from the decomposition of electrolyte.
If the electrolysis is with more than one cation & anion then all the ions are not discharged while it’s done
in accordance to their preferential discharging tendency i.e. the ion which requires lesser energy or lesser
discharge potential will be discharged.

The potential at which the ion is discharged at their respective electrode is called discharging potential.

The decreasing order of discharge potential,

For cations, K +  Na +  Ca 2+  Mg 2+  Al 3+  Zn 2+  Fe 2+  Pb 2+  H +  Cu 2+  Ag +

For anions, SO 24−  NO 3−  OH −  Cl −  Br −  I −

Example: Electrolysis of an aqueous solution of NaCl

Nacl ⇌ Na+ + Cl−

H2 O ⇌ H + + OH −

25
JMD ੴ

At cathode :- Both Na+ and H+ goes to cathode, since the discharge potential of H+ is lower in preference
to Na+, thus, H+ ions are discharged.

H + + e − → H (Reduction, Primary Change)

H + H → H 2 (Secondary Change)

Thus, H2 gas evolved at cathode and Na+ Remains in solution.

At Anode, Both Cl- and OH- ions goes to anode, since Cl- has lower discharge potential than that of OH-
ions, thus, Cl- ions one discharged.

Cl − + e − → Cl (Oxidation, Primary Change)

Cl + Cl → Cl 2( g ) (Secondary Change)

Thus, Cl2 gas is evolved at anode while OH- Remains in the solution.

TYPE III: REACTIVE ELECTRODE AND MOLTEN OR AQUEOUS ELECTROLYTE

Example: Electrolysis of aq. CuSO4 and copper electrodes

CuSO4 → Cu 2+ + SO42−
H 2 O → H + + OH −
At Anode, Both OH- and SO 24 − reaches anode but though OH- has lower discharging potential but still
anode i.e. Cu itself undergoes oxidation as its metallic in nature and oxidation of metal is a much
spontaneous process.
Cu ( s ) → Cu 2(+aq ) + 2e −
At Cathode, Among Cu2+ and H+, Cu2+ due to its lower discharge potential undergoes discharging via
Reduction.
Cu 2+( aq ) + 2e − → Cu ( s )

26
JMD ੴ

➢ QUANTITATIVE ANALYSIS OF ELECTROLYSIS

FARADAY’S LAWS OF ELECTROLYSIS

First Law

The Amount of Electrolysis (chemical Reaction) and Mass Deposition at cathode or liberation at Anode is
directly proportional to the quantity of electricity passed though the electrolyte.

WαQ
W=ZxQ (Where Z = Constant Called electrochemical Equivalent)
W=ZxIxt

SECOND LAW

When the same amount of charge is passed through different electrolytes, then the masses of different
substances deposited at their respective electrodes will be in the ration of their equivalent masses.

E/96500 = Z

So, if E1/96500 = Z1 and E2/96500 = Z2

Then, Z1/Z2 = E1/E2

NOTE: The value of Z can also be calculate by Z = E/96500 ex, For Ag, The Equivalent Mass = 108/1 and
on putting the value of E, Z = 108/1/96500 ≈ 0.001118 g/c which is the some mass deposits when 1 ampere
of current passes through 1 sec

Molar Mass
NOTE: Equivalent weight (E) =
A/B/C/n/v

Equivalent weight of a substance depends on the nature of chemical reaction in which the substance takes
part equivalent weight of anode or base.

• E acid =
Molecular weight
Basicity

Basicity Means, No. of H atoms replaced from one Molecule of acid.

• E acid =
Molecular weight
Acidity
Acidity = No. of OH groups replaced from one Molecule of base

63 98
Example, E = , E =
HNO 1 H SO 2
3 2 4

40 74
E = , E =
NaOH 1 Ca(OH ) 2
2

27
JMD ੴ

Atomic Wei ght

• E Element =
Valency of atom
Malulav Mass
• E ionic =
Charge on cation or anion

➢ APPLICATION OF ELECTROLYSIS

1. For Electrolytic extraction of metals like Na, K, Mg, Ca etc.

2. Production of Cl2 or H2 from NaCl or two respectively.
3. Electroplating
4. For the calculation of equivalent masses of elements.

➢ PART-II ELECTROCHEMICAL CELLS

A device used to convert the chemical energy produced in a redox reaction into electrical energy is called
electro chemical cell. These cells are also referred as galvanic cells, voltaic cells or Daniel cells

➢ GALVANIC / VOLTAIC CELL;

When two half cells i.e., Zn oxidation half cells and Cu reduction half cells are connected then the following
observations are noted.

• There will be a dynamic equilibrium at each half cells before they are not in contact but the moment
they will be connected, surplus e- (extra electron) at oxidation electrode (anode) of Zn are transferred
to Cu reduction electrode which is electron deficient and both becomes neutral while the further
oxidation and reduction at both half cells is also initiated due the movement of electron via external
circuit as the opposition caused by the electrode is eliminated.
• Soon, due to excessive ions at both half cells, again the further oxidation and reduction will stop,
which can again be initiated by the removal of excessive ions with the help of an inverted U tube
called salt bridge, which allows the movement of ions from one solution to other without mixing of
two solutions. Thus, whereas, electron flows in the outer circuit in wire while the inner circuit is
completed by the flow of ions between the half cells via salt bridge.

28
JMD ੴ

At Anode: Zn → Zn 2+ + 2e − (E zn / zn 2 + )
At Cathode: Cu 2+ + 2e − → Cu (E cu2+ / Cu ) )
Zn + Cu 2+ → Zn 2+ + Cu (Ecell)

E cell = E Zn/Zn 2+ + ECu 2+ / Cu

In order to make it simpler, we discussed all the potentials in reduction potential for which oxidation will
be the (-) of its reduction potential.

Thus, E 0Zn/Zn (oxidation Potential) = − E 0Zn

2+ 2+
/ Zn
(Reduction Potential)

 E cell = − E 0Zn 2 + / Zn + E Cu
0
2+
/ Cu

0
E Cu 2+
/ Cu
− E 0Zn2 + / Zn

Nernst Equation for the above reaction:-

0.059 [ Zn 2+ ][Cu]
E cell = E 0 cell − log
n [Cu 2+ ][Zn]

As [Cu] = [Zn] = 1, in solid state,

0.059 [ Zn 2+ ]
 E cell = E 0 cell − log
n [Cu 2+ ]

In general,

0.059 [0]
E (cell) = E 0 (cell) − log
n [ R]

➢ SUMMARY:
• Electron flows from Zn anode (-) to Cu cathode (+) while current flows in opposite direction
conventionally from (+) cathode to anode (-) through external circuit.
• Oxidation of Zn produces excess of Zn2+ while reduction of Cu2+ causes excess of SO42- ions which
moves through the salt bridge in inner circuit.
• With the time, Cu2+ from CuSO4 reduced to Cu and SO42- migrates through salt bridge, concentration
of CuSO4 decreases. Also, all the Zn will oxidised and no more oxidisable Zn will be left, in both cases
the current falls with time and becomes zero at a definite time.
• If an external opposite potential is supplied to the cell, the cell will works till the external EMF becomes
equal to Ecell and at this time current becomes zero and on further increasing the external EMF, the
reaction reverse in opposite direction i.e., oxidation of Cu takes place reduction of Zn as in electrolytical
cell in which the external EMF drives a non-spontaneous reaction.

Therefore, Ecell = Ecathode - Eanode or Eright - Eleft

29
JMD ੴ

• For the set up in such cell, a word LOAN can be memorised for oxidation half cell like for Zn electrode
(L=left, O=oxidation, A=anode and N=negative) while the opposite is for reduction Cu
electrode.(R=right, R=reduction, C=cathode and P=positive)
• In Daniel cell, Salt bridge is replaced by a porous pot through which excess SO42− of Cu half-cell
transferred to the ZnSO4 half cell

An electrochemical cell is represented as:-

Metal/Metal ion (Conc.) || Metal Ion (Conc.)/ Metal

Salt
bridge Cathode
Anode

For Galvanic Cell: - Zn/Zn2+ (1M) || Cu2+ (1M)/Cu

• At equilibrium with the passage of time, the conc. of CuSO4 kept on decreasing, ZnSO4 Increasing,
there will be a time when current stops flowing, Ecell become Zero, the concentration of ions (Zn2+ &
Cu2+) become constant.
2+
[Zn ]
Thus, = Kc and Ecell = 0
2+
[Cu ]

Putting these values in Nernst equation,

0.059 [Zn 2+ ]
Ecell = E 0 cell − log
n [Cu 2+ ]
0.059
0 = E 0cell − log Kc
n
0.059
E 0 cell = log Kc, at 298K
n

➢ CELL POTENTIAL AND GIBB’S FREE ENERGY:

G = - nFE
cell
For, maximum obtainable work, E should be Max, which is at standard conditions i.e. E0.
 G = −nFE 0cell
Now, as at Equilibrium,
0 RT
E cell = 2.303 log Kc
nf
On substituting the value of E0cell
 RT 
 G = − 2.303 log Kc 
 nF 
 ΔG = -2.303 RTlog Kc

30
JMD ੴ

➢ DIFFERENCE BETWEEN ELECTROLYTIC CELL & ELECTROCHEMICAL CELL

➢ ELECTROCHEMICAL SERIES:
In the similar manner, the reduction potentials at different electrodes can be calculated and if the values are
arranged in increasing order of reduction potentials or decreasing order of oxidation potentials. A series
will be obtained referred as Electrochemical Series.

Application of electrochemical series:

1) To compare the relative reactivity’s of different elements. The elements with high negative values
are the most reactive metals while elements with high positive values shows lower metallic and
higher non-metallic character.

31
JMD ੴ

2) In other words we can also say, on moving down the group, metallic character decreases which
means tendency of getting oxidizing decreases and decreasing strength as reducing agent or
increasing strength of oxidising agent.
3) As, non-metallic character increases, tendency of getting reduced increases. And thus, the strength
of reducing agent decreases.
4) It’s also used for the calculation of EMF of any cell.

➢ PART-III CONDUCTANCE OF ELECTROLYTIC SOLUTIONS

Solutions which conduct electricity and undergo decomposition when current is passed through them are
electrolytic conductors or electrolytes.
The hindrance provided by the solutions on passage of current is called resistance (R) having unit ohm (Ω).
The reciprocal of resistance is conductance i.e. the ease to which the current flows through an electrolyte.
It’s denoted by G and the unit is mho (Ω-1) or Siemens (S).
G = 1/R
Resistance can be measured with the help of whetstone’s bridge. Electrical resistance is directly
proportional to its length and inversely proportional to its cross sectional area.

The constant of proportionality, ρ (Greek, rho), is called resistivity (specific resistance). Its SI units are
ohm meter. The resistivity for a substance is its resistance when it is one meter long and its area of cross
section is one m2.
The inverse of resistivity, called conductivity (specific conductance) is represented by the
Symbol, қ (Greek, kappa). Conductivity of a material is in S m–1 it’s the conductance when it is 1 m long
and its area of cross section is 1 m2.

And we know that

Where G* = cell constant by putting the values

R = G*/ қ

i.e. қ = G × G*
Specific conductivity = conductance × cell constant

32
JMD ੴ

➢ VARIATION OF MOLAR CONDUCTIVITY WITH CONCENTRATION

Conductivity always decreases with decrease in concentration both, for weak and strong electrolytes. This
can be explained as the number of ions per unit volume that carry the current in a solution decreases on
dilution.

STRONG ELECTROLYTES

Strong electrolytes ionizes completely in aqueous solutions thus, they have high conductance. With dilution,
the interionic forces are expected to decrease so, the ionic mobility increases results an increase in molar
conductance. This increase in molar conductivity will continue up to a point when the interionic forces
become negligible and further increase in dilution does not changes the molar conductivity. This is known
as limiting molar conductivity or molar conductivity at infinite dilution
For strong electrolytes, Debye-Onsager equation is followed:
˄m = ˄mo - A√c

WEAK ELECTROLYTES

Here with dilution the increase in the molar conductance is quiet large as
dilution helps in dissociation, moreover on dilution undissociated
molecules which causes hindrance in the path of conductance also decrease
which resulting in the increase in conductance.
As in the graph the curve of CH3COOH (weak electrolyte) shows a large
variation compared to KCl (strong electrolyte).
However, for weak electrolytes molar conductivity increases sharply near
high dilution. Hence, experimentally it’s not possible to calculate it
although the ionization is complete but the number of ions per unit volume
is very low.
This problem is solved by kohlrausch law.

➢ KOHLRAUSCH LAW
The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and cation of the electrolyte. In general, if an electrolyte on dissociation
gives λ+ cations and λ– anions then its limiting molar conductivity is given by:

Λ0 m = λ0cations + λ0anions

At any concentration c, if α is the degree of dissociation then it can be approximated to the ratio of molar
conductivity Λm at the concentration c to limiting molar conductivity, Λ0 m Thus we have:

33
JMD ੴ

, where ka is the dissociation constant

APPLICATIONS OF KOHLRAUSCH LAW

Using Kohlrausch law of independent migration of ions, it is possible to calculate molar conductivity and
equivalent conductivity of weak electrolytes at infinite concentration.
Also, as mentioned above it also helps us to calculate the degree of dissociation and dissociation constant

➢ BATTERIES
(A) Primary Cells (B) Secondary Cells (C) Fuel Cells.

(A) Primary Batteries: In the primary batteries, the reaction occurs only once and cannot be reused again.
Two common examples of this type are dry cell and mercury cell.

➢ Dry Cell: A dry cell is a compact form of leclanche cell used in the clocks and transistors. The cell
consists of a zinc container that also acts as anode and the cathode is a carbon (graphite) rod surrounded
by powered manganese dioxide and carbon. The space between the electrodes is filled by a moist paste
of ammonium chloride (NH4Cl) and zinc chloride (ZnCl2) which works as an electrolyte. These cells
have voltage in the range of 1.25 to 1.50 V. However, these cells do not have a long life because the
acidic NH4Cl corrodes the zinc container even when the cell is not in the use.
Anode: Zn (s) → Zn 2+ + 2e −
Cathode: MnO 2 + NH +4 + e − → MnO (OH ) + NH 3

➢ Mercury Cell: It’s used in the small electrical devices like hearing aids and the wrist watches as it gives
a constant voltage of 1.25V. it consists zinc container that acts as anode and the cathode ids a carbon
rod Moist mercuric oxide mixed with KOH is used as electrolyte. A lining of porous paper keeps the
electrolyte separate from the zinc anode.
Anode: Zn (Hg ) → 2OH − + ZnO (s) + H 2 O + 2e −
Cathode: HgO + H 2 O + 2e − → Hg + 2OH −

(B) Secondary Batteries: A Secondary cell after use can be recharged by passing current through it in the
opposite direction so that it can be used again. Two important examples are lead storage batteries and
nickel cadmium batteries.

➢ Lead Storage Battery: The most important secondary cell is the lead storage battery commonly used
in automobiles and invertors. It consists of a lead anode and a grid of lead packed with lead dioxide
(PbO2) as an electrolyte. To increase the output of each cell, the cathode and anode plates are connected
together (in the alternate positions) in parallel i.e. anode to anode and cathode to cathode. To have an
output voltage of 12V, six such cells are connected in series.
The cell reactions when the battery is in use are given below:
Anode: Pb(s) + SO 24− (aq ) → PbSO 4 (s) + 2e −

34
JMD ੴ

Cathode: PbO 2 (s) + SO 24− (aq) + 4H + (aq) + 2e − → PbSO 4 (s) + 2H 2 O (l)

On charging the battery the reaction is reversed and operated like an electrolytic cells i.e. now electrical
energy is supplied to it from an external source. Such operations are only possible because pbSO4
formed during discharge is a solid and sticks to the electrodes. It’s therefore in the position to either
receive or give up electrons during electrolysis and moreover, during recharging PbSO4(s) on anode and
cathode is reversed and converted into Pb and PbO2, respectively.

➢ Nickel Cadmium Batteries: It’s widely used in the calculators. It has a longer life than lead storage
batteries but it’s more expensive. It consists of a cadmium electrode as anode and a metal grid containing
nickel oxide as cathode is immersed in KOH solution.

Anode: Cd + 2OH − → Cd (OH ) 2 + 2e −

Cathode: NiO 2 + 2H 2 O + 2e − → Ni(OH) 2 + 2OH -

(C) Fuel Cells: Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen,
methane, methanol, etc. directly into electrical energy are called fuel cells. One of the most successful
fuel cell, the hydrogen-oxygen fuel cell which is used as a primary source of electrical energy on the
Apollo moon flights.
It consists of porous carbon electrodes containing suitable catalysts (finely divide Pt or Pd) incorporated
in them for increasing the rate of electrode reactions. Concentrated NaOH or KOH solutions are placed
between the electrodes to act a s electrolyte. Hydrogen and oxygen gases are bubbled through the porous
electrodes into the KOH/NaOH solution. It has a great advantage as gaseous materials are easy to supply
and consume thus due to this continuous supply such cells are never become dead and can gives a
potential of 0.9V, moreover with their good efficiency over thermal power plants they also does not
causes any pollution. Their disadvantage includes the high cost and the problem of dealing gaseous
fuels.

Anode: 2H 2 + 4OH − → 4OH − + 4e −

Cathode: O 2 + 2H 2 O + 4e − → 4OH -

➢ CORROSION
The theory of corrosion can be explained by taking an example of rusting of iron. The theory is called
electrochemical theory because it explains the formation of rust on the basis of the formation of
electrochemical cell on the surface of the metal.

Rusting of Iron Involves the following steps:

Step 1: Water vapours present in contact with iron surface contains CO2

H 2 O + CO 2 → H 2 CO 3 (Carbonic Acid)

+ 2−
H 2CO3  2H + CO (Ionization of carbonic acid)
3

35
JMD ੴ

Step 2: Oxidation of iron at a particular spot (generally, at the point of Strain), known as anodic spot

Fe → Fe 2 + + 2e − (Oxidation, At Anode)

Further, this Fe2+ reacts with O2 and H2O to from ferric oxide which further gets hydrated to from rust

4 Fe 2 + + O 2 + 4 H 2O → 2 Fe 2 O 3+ 3 H +

Fe 2 O 3 + x H 2 O → Fe 2 O3.x H 2 O
( Rust )

Step 3: Electrons from Anodic spot flows to another spot with impurities to reduce O2, known as cathode
spot

O 2 + 1H 2 O + 4e − → 4OH − (Reduction, At cathode)

Control of Corrosion
Since both the cathodic and anodic steps must take place for corrosion to occur, prevention of either one
will stop corrosion. The most obvious strategy is to stop both processes by coating the object with a paint
or other protective coating.

Sacrificial coatings
One way of supplying this negative charge is to apply a coating of a more active metal. Thus a very common
way of protecting steel from corrosion is to coat it with a thin layer of zinc; this process is known as
galvanizing. The zinc coating, being less noble than iron, tends to corrode selectively.

Cathodic Protection
A more sophisticated strategy is to maintain a continual negative electrical charge on a metal, so that its
dissolution as positive ions is inhibited. Since the entire surface is forced into the cathodic condition, this
method is known as cathodic protection. The source of electrons can be an external direct current power
supply (commonly used to protect oil pipelines and other buried structures), or it can be the corrosion of
another, more active metal such as a price of zinc or aluminum buried in the ground nearby.

36
JMD ੴ

SECTION 1: ELECTROCHEMICAL CELLS

1. The standard electrode potential (E0) for Daniell cell is +1.1 V. Calculate the Δ G 0 for the reaction.
2 2+ -1
Zn(s) + Cu (aq) → Zn (aq) + Cu(s) (1F = 96500 C mol )
2. Can you store copper sulphate solution in a zinc pot?
3. Give the standard electrode potentials,
+ +
K /K = −2.93V, Ag /Ag = 0.80V
2+ 2+
Hg /Hg = 0.79V, Mg /Mg = -2.37V ,
3+
Cr /Cr = −0.74V
Arrange these metals in their increasing order of reducing power.
4. Calculate the emf of the cell in which the following reaction takes place
+ 2+
Ni (s) + 2Ag (0.002M ) → Ni (0.160M ) + 2Ag (s )

Given that E 0cell = 1.05 V

5. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
6. Zinc rod is dipped in 0.1 m solution of ZnSO4. The salt is 95% dissociated at this dilution at 298 K.
calculate the electrode potential.
7. Write the Nernst equation and emf of the following cell at 298 K.
i. Mg (s) | Mg 2+ (0.001M ) || Cu 2+ (0.0001 M ) | Cu (s)
ii. Fe(s) | Fe 2+ (0.001M) || H + (1M) | H 2 (g)(1bar ) | Pt (s)
Give that, E 0Mg 2 + Mg = −2.36 V

E 0Cu 2 + Cu = 0.34 V, E 0Fe2 + Fe = −0.44 V

8. How would you determine the standard electrode potential of the system Mg2+ / Mg?
9. The cell in which the following reaction occurs,
2Fe 3+ (aq ) + 2I − (aq ) → 2Fe 2+ (aq ) + I 2 (s) has E 0cel = 0.236 V at 298 K,Calculate the standard Gibbs
energy and the equilibrium constant of the cell reaction.
10. Calculate the emf of the following cell at 250C
Ag (s) | Ag + (10 −3 M ) || Cu 2+ (10 −1 M ) | Cu (s) Given, E 0cel = +0.46 V and log 10n = n.
11. In the button cells, widely used in watches and other devices, the following reaction takes place
Zn (s) + Ag 2 O(s) + H 2 O(l) → Zn 2+ (aq ) + 2Ag (s) + 2OH − (aq ) Determine E0 and 0
Δ G for the

reaction. (Given, E 0Ag + / Ag = +0.80 V, E 0Zn 2 + / Zn = −0.76 V

12. A copper-silver cell is set up. The copper ion concentration is not known. The cell potential when
measured was 0.422 volt. If the concentration of silver is 0.10M. Calculate the concentration of
Cu.(Given E0 Ag+\Ag = 0.80V and E0Cu2+\Cu = 0.34 volt).
13. Find the stability constant of the complex [Zn(NH3)4]2+ formed in the reaction,
Zn 2+ + 4 NH 3 ⇌ [ Zn ( NH 3 ) 4 ] 2+ Given that, E 0Zn / Zn = −0.76 V and E 0 [ Zn ( NH 3 ) 4 ] 2+ / Zn ,4 NH 3 = −1.03V
2+

37
JMD ੴ

Long Answer Questions

1. Calculate the standard cell potentials of galvanic cell in which the following reactions take place:
i. 2Cr (s) + 3Cd 2+ (aq ) → 2Cr 3+ (aq ) + 3Cd
ii. Fe 2+ (aq ) + Ag + (aq ) → Fe 3+ (aq ) + Ag (s)

Calculate the Δ G 0 and equilibrium constant for the reactions.

r

2. The following half-cell reactions are given,

i. Cu 2+ (aq) + e − → Cu + (aq); E 0 = 0.15V
ii. 2H + (aq ) + 2e − → H 2 (aq ); E 0 = 0.00 V
iii. CuI ( s ) + e − → Cu ( s) + I − (aq); E 0 = −0.17V
iv. Zn 2+ (aq ) + 2e − → Zn (s); E 0 = −0.76 V

Calculate the voltage of the cell Zn|Zn2+(1M) || I- (1 M) | CuI + Cu (Ans E0 = 2.50V).

3. For the half-cell reactions, Cu 2+ + e − → Cu + ; E 0 = 0.15V

Cu 2+ + 2e − → Cu ; E 0 = 0.34 V

Calculate E0 of the half-cell reaction and predict whether Cu+ undergoes disproportionation or not.
(Ans. E0 = +0.53 V)

4. Calculate the pH using the following cell: Pt(H 2 ) | H + ( xM) || H + (1M) | Pt(H 2 ) if Ecell = 0.2364 V. (Ans.
1atm 1atm

pH = 4)
SECTION 2: PROPERTIES OF A ELECTROLYTIC CELL

Very short Answer Questions

1. Why is alternating current used for measuring resistance of an electrolytic solution?

2. With the help of a graph explain why it is not easy to determine om for a weak electrolyte by
extrapolating the concentration – molar conductance curve as for strong electrolytes.
3. Why does the conductivity of a solution decrease with dilution?
4. Suggest a way to determine the Λ0𝑚 value of water.
5. If specific conductivity of N/50 KCl solution at 298 K is 0.002765 Ω-1 cm-1 and resistance of a cell
containing this solution is 100 Ω, calculate the cell constant. (0.2765 cm-1)
6. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm -1. Calculate its molar
conductivity. (12.4 S Cm2mol-1)
Short Answer Questions:

1. For a weak electrolyte, its molar conductance in dilute solution increases sharply as its concentration
in solution is decreased. Explain.
2. State Kohlrausch law of independent migration of ions. Why the conductivity of a solution does
decreases with dilution?

38
JMD ੴ

3. The measured resistance of a conductance cell containing 7.5 x 10-3 M solution of KCl at 25o C was
1005 ohm. Calculate specific conductance and molar conductance of the solution. Cell Constant =
1.25/cm
4. The conductivity of 0.001 M acetic acid is 4 x 10-5 S/cm. calculate the dissociation constant of acetic
acid, if molar conductivity at infinite dilution for acetic acid is 390 S cm2/mol.( 1.18 x 10-5)
5. The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500 Ω. What is
the cell constant if the conductivity of 0.001 M KCl solution at 298 K is 0.146 x 10-3 S cm-1? (0.219
Cm-1)
6. The molar conductivity of 0.025 mol L-1 methanoic acid is 46.1 S cm2 mol-1. Calculate its degree of
dissociation and dissociation constant.
Given, 0 + 2 −1
λ (H ) = 349.6 S cm mol

And λ 0 (HCOO − ) = 54.6 S cm 2 mol − 1 (α = 0.114 and Ka = 3.67 x 10-4 mol L-1)
7. From the following molar conductivities at infinite dilution.
 mo for Ba(OH) 2 = 457 .6 −1cm 2 mol −1
 mo for BaCl 2 = 240 .6 −1cm 2 mol −1
 mo for NH 4 Cl = 129 .8 −1cm 2 mol −1
Calculate  mo for NH4 OH.
8. The resistance of a conductivity cell when filled with 0.05 M solution of an electrolyte x is 100 Ω
at 400 C, The same conductivity cell filled with 0.01 M solution of electrolyte y has a resistance of
50 Ω. The conductivity of 0.05 M solution of electrolyte x is 1.0 x 10-4 S cm-1..
Calculate
i. Cell constant.
ii. Conductivity of 0.01 M y solution
iii. Molar conductivity of 0.01 M y solution
Long Answer Question

1. Conductivity of 0.00241 M acetic acid is 7.896 x 10-5 S cm-1. Calculate its molar conductivity. If
Λ0𝑚 acetic acid is 390.5 S cm2 mol-1, what is its dissociation constant? (1.7 x 10-5 mol L-1)
2. Conductivity of two electrolyte solutions A and B each having a concentration of 0.1 M are 8.5 x
10-2 and 4.1 x 10-4 S cm-1 respectively. Which of the two offers less resistance to the flow of current?
3. The Λ0𝑚 value forNaCl and KCl are 126.5 and 149.9 Ω-1 cm2 mol-1 respectively. The ionic
conductance of Na+ at infinite dilution is 50.1 Ω-1 cm2 mol-1. Calculate the ionic conductance at
infinite dilution for K ion.
SECTION 3 : ELECTROLYSIS

Very Short Answer Questions

1. How much charge is required for the reduction of 1 mole of Cu2+ to Cu?
2. When acidulated water (dil. H2SO4) is electrolysed, then pH of the solution be affected? Justify your
answer.
3. State the products of electrolysis obtained on thre cathode and the anode, when an aqueous solution
of AgNO3 with silver electrodes used.

39
JMD ੴ

Short Answer Questions

1. Consider the reaction,

Cr2 O 72− + 14 H + + 6e − → 2Cr 3+ + 7 H 2 O

What is the quantity of electricity in coulombs needed to reduce 1 mole of Cr2 O 72 − ?

2. What is amount of charge required to carry out the conversion of 1 mole of Al3+ ions to Al according
to the following reaction?
Al 3+ + 3e − → Al
Or
How much charge is required for the following reduction 1 mole of Al3+ to Al?
3. If a current of 0.5 A flow through a metallic wire for 2 h, then how many electrons would flow
through the wire? (Ans 2.250 x 1022)
4. A current of 1.70 A is passed through 300.0 mL of 0.160 M solution of ZnSO4 for 230 s with a
current efficiency of 90 per cent. Find out the molarity of Zn2+ after the deposition of zinc. Assume
the volume of the solution to remain constant during electrolysis. (Ans 00.154 M)
5. How much electricity is required in coulomb for the oxidation of
i. 1 mole of H2O to O2? (1.93 x 105 C)
ii. 1 mole of FeO to Fe2O3? ( 96500 C)
6. A Solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 A for 20
min. What mass of Ni is deposited at the cathode? (Ans 1.825 g)
7. Silver is electrodeposited on a metallic vessel of total surface area 900 cm2 by passing a current of
0.5 A for 2 h. Calculate the thickness of silver deposited. Given density of silver = 10.5 g cm-1.
Atomic mass of silver = 108 amu. F = 96500 C mol-1. (Ans 4.23 x 10-4 cm)
Long Answer Questions

1. Three electrolytic cells A, B c containing solutions of zinc sulphate, silver nitrate and copper
sulphate, respectively are connected in series. A steady current of 1.5 A was passed through them
until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow? What mass
of copper and zinc were deposited in the concerned cells? (Atomic mass, Ag = 108, Zn =65.4, Cu =
63.5)
2. Predict the products of electrolysis in each of the following:
i. An aqueous solution of AgNO3 with silver electrodes.
ii. An aqueous solution of AgNO3 with platinum electrodes.
iii. A dilute solution of H2SO4 with platinum electrodes.
iv. An aqueous solution of CuCl2 with platinum electrodes.
3. Silver is electrodeposited on a metallic vessel of surface area 800 cm2 by passing a current of 0.20
A for 3.0 h. Calculate the thickness of silver deposited, given its density as 10.47 g/cc.[Atomic mass
of Ag = 107.92] (Ans. 2.88 x 10-4 cm)
4. From the value of Faraday (96500 C) and Avogadro (6.023 x 1023), we calculate the coulomb charge
on an electron. (Ans. 1.6 x 10-19 C)
5. Two electrolytic cells containing silver Nitrate solution and dilute sulphuric acid solution were
connected in series. A steady current of 2.5Amp was passed through them till 1.078 gms of silver
was deposited

40
JMD ੴ

a. How much electricity was consumed?

b. What was the weight of oxygen gas liberated?
6. How many grams of silver could be plated out on a serving tray by electrolysis of a solution
containing silver in +1 oxidation state for a period of 8.0 h at a current of 8.46 A ? What is the area
of tray if the thickness of the silver plating is 0.00254 cm? Density of silver is 10.5 g/cm 3. (Ans.
1.02 x 104 cm2)
7. Molten aluminium chloride is electrolyzed with a current of 0.5 A to produce 27.0 g of aluminium
i. How many gram equivalents of aluminium were produced?
ii. How many gram atoms of aluminium were produced?
iii. How many atoms of aluminium were produced?
[Atomic mass of Al = 27 , Avogadro number = 6.02 x 1023]
8. Electric current is passed through two cells A and B in series. Cell A contains aqueous solution of
Ag2SO4 and platinum electrodes. Cell B contains aqueous solution of CuSO4 and copper electrodes.
The Current is passed till 1.6 g of oxygen is liberated at the anode in ce;; A. Calculate the quantities
of copper and silver deposited at the cathode of the two cells. [Atomic mass, O = 16, Cu = 63.5, Ag
= 108]
9. How much time would it take in minutes to deposit 1.18 g of metallic copper on a metal object when
a current of 2.0 A is passed through the electrolytic cell containing Cu=2+ ions? [Cu=63.5 g mol1 ,
1 F = 96,500 C mol-1]

41
 ➢ EXEMPLAR QUESTIONS
1) Which cell will measure standard electrode
potential of copper electrode?
a) Pt(s)│H2(g, 0.1 bar)│H+ (aq.,
1M)║Cu2+(aq.,1M)│Cu
b) Pt(s)│H2(g, 1 bar)│H+ (aq.,
1M)║Cu2+(aq.,2M)│Cu
c) Pt(s)│H2(g, 1 bar)│H+ (aq.,
1M)║Cu2+(aq.,1M)│Cu
d) Pt(s)│H2(g, 1 bar)│H+ (aq.,
0.1M)║Cu2+(aq.,1M)│Cu
4) The difference between the electrode potential
2) Electrode potential for Mg electrode varies
according to the equation
3) Which of the following statement is correct?
a) Ecell and ∆rG of cell reaction both are
extensive properties.
b) Ecell and ∆rG of cell reaction both are
intensive properties.
c) Ecell is an intensive properties while ∆rG
of cell reaction is an extensive properties.
d) Ecell is an extensive properties while ∆rG
of cell reaction is an intensive properties.
of two electrodes when no current is drawn
through the cell is called :

E =E
Θ
−
0.059
log
1 . The graph of
Mg2+|Mg Mg2+|Mg 2 2+
[Mg ] a) Cell potential
EMg2+│Mg versus 2+
log [Mg ] is: b) Cell emf
c) Potential difference
a) d) Cell voltage

5) Which of the following statement is not correct

EMg2+/Mg

about an inert electrode in a cell ?

a) It does not participate in the cell reaction
b) It provides surface either for oxidation or
for reduction reaction
Log [Mg2+] c) It provides surface for conduction of
b) electrons
d) It provides surface for redox reaction
EMg2+/Mg

6) An electrochemical cell can behave like an

electrolytic cell when :
Log [Mg2+] a) Ecell = 0
b) Ecell > Eext.
c) c) Eext. > Ecell
EMg2+/Mg

d) Ecell = Eext.

7) Using the data given below find out the strongest

reducing agent.
Log [Mg2+] E0Cr2O7/Cr3+ = 1.33V
d) E0Cl2/Cl- = 1.36 V
E0MnO4-/Mn2+ = 1.51 V
EMg2+/Mg

E0Cr3+/Cr = -0.74 V
a) Cl-
b) Cr
c) Cr3+
d) Mn2+
Log [Mg2+]
 JMD ੴ

8) Use the data given in Q. 8 and find out which of b) 

0
+
0
−
0
m(NH Cl) m(NaOH) m(NaCl)
the following is the strongest oxidizing agent. 4

a) Cl- c) 
0
+
0
−
0
m(NH Cl) m(NaCl) m(NaOH)
b) Mn2+ 4

c) MnO4- d) 
0
+
0
−
0
m(NaOH) m(NaCl) m(NH Cl)
4
d) Cr3+

15) In the electrolysis of aqueous sodium chloride

9) Use the data given in ques.8 find out in which
solution which of the half cell reaction will occur
option the order of reducing power is correct.
at anode?
a) Cr3+ < Cl- < Mn2+ < Cr
b) Mn2+ < Cl- < Cr3+ < Cr
a) Na+ (aq) + e- → Na(s) : E0cell = -
c) Cr3+ < Cl- < Cr2O72- < MnO4-
2.71 V
d) Mn2+ < Cr3+ < Cl- < Cr
b) 2H2O (l) → O2 (g) + 4H+ (aq) + 4e-
E0cell =
10) Use the data given in ques.8 find out the most
1.23V
stable ion in its reduced form.
c) H+ (aq) + e- → ½ H2 (g); E0cell =
a) Cl-
0.00V
b) Cr3+
d) Cl- (aq) → ½ Cl2 (g) + e; E0cell =
c) Cr
1.36 V
d) Mn2+
II. Multiple Choice Questions
11) Use the data given in ques.8 find out the most
stable oxidised species.
a) Cr3+ 16) The positive value of the standard electrode
b) MnO4- potential of Cu2+/Cu indicates that :
c) Cr2O72- a) This redox couple is a stronger reducing
d) Mn2+ agent than the H+/H2 couple
b) This redox couple is stronger oxidising
12) The quantity of charge required to obtain one agent than the H+/H2 couple
mole of aluminium from Al2O3 is : c) Cu can displace H2 from acid
a) 1F d) Cu cannot displace H2 from acid
b) 6F
c) 3F 17) E0cell for some half-cell reactions are given
d) 2F below. On the basis of these mark the correct
answer.
13) While charging the lead storage battery :
a) PbSO4 anode is reduced to Pb A) H+ (aq) + e- → ½ H2 (g); E0cell =
b) PbSO4 cathode is reduced to Pb 0.00V
c) PbSO4 cathode is oxidised to Pb B) 2H2O (l) → O2 (g) + 4H+ (aq) + 4e-
d) PbSO4 anode is oxidised to PbO2 E0cell =
1.23V
14) 
0 Is equal to : C) 2SO4 (aq) → S2O8 (aq) + 2e- E0cell
2- 2-
m (NH4OH)
=1.96V
a) 
0
+
0
−
0
m(NH OH) m(NH Cl) m(HCl)
4 4

43
 JMD ੴ
a) In dilute sulphuric acid solution, hydrogen
will be reduced at cathode
b) In concentrated sulphuric acid solution,
water will be oxidised at anode
c) In dilute sulphuric acid solution, water will
be oxidised at anode
d) In dilute sulphuric acid solution, SO42- ion
will be oxidised to tetrathionate ion at
anode
18) E0cell = 1.1V for Daniell cell. Which of the
following expressions are correct description of
state of equilibrium in this cell?
a) 1.1 = Kc
b) 2.303 RT/2F log Kc = 1.1
c) log Kc = 2.2/0.059
d) log Kc = 1.1
19) conductivity of an electrolytic solution depends
on :
a) nature of electrolyte
b) concentration of electrolyte
c) power of AC source
d) distance between the electrodes
20) What will happen during the electrolysis of
aqueous solution of CuSO4 by using platinum
electrodes?
a) Copper will deposit at cathode
b) Copper will deposit at anode
c) Oxygen will be released at anode
d) Copper will dissolve at anode
21) What will happen during the electrolysis of
aqueous solution of CuSO4 in the presence of
Cu electrode?
a) Copper will deposit at cathode
b) Copper will deposit at anode
c) Oxygen will be released at anode
d) Copper will dissolve at anode
22) Molar conductivity of ionic solution depends on:
a) Temperature
b) Distance between electrodes
c) Concentration of electrolytes in solution
d) Surface area of electrodes
SHORT QUESTIONS:
23) Aqueous copper sulphate solution and aqueous
silver nitrate solution are electrolysed by 1A
current for 10 min. in separate electrolytic cells.
Will the mass of copper and silver deposited on
cathode be same or different? Explain your
answer.
24) Depict the galvanic cell in which the cell
reaction is Cu + 2Ag+ → 2Ag + Cu2+
25) Why is alternating current used for measuring
resistance of an electrolytic solution?
26) A galvanic cell has electrical potential of 1.1V.
If an opposing potential of 1.1V is applied to this
cell, what will happen to the cell reaction and
current flowing through the cell?
27) How will the pH of brine (aq. NaCl solution) be
affected when electrolysed?
28) Unlike dry cell, the mercury cell has a constant
cell potential throughout its useful life. Why?
29) Solutions of two electrolytes ‘A’ and ‘B’ are
diluted. The  m of ‘B’ increases 1.5 times while
that of A increases 25 times. Which of the two is
a strong electrolyte? Justify your answer.
30) When acidulated water (dilute H2SO4 solution)
is electrolysed, will the pH of the solution be
affected? Justify your answer.
31) What advantage do the fuel cells have over
primary and secondary batteries?
32) Write the cell reaction of a lead storage battery
when it is discharged. How does the density of
44
JMD ੴ

the electrolyte change when the battery is ➢ SOLUTIONS (EXEMPLAR

discharged? PROBLEMS)
1) (C) Potential of an electrode when the electrode
33) Why on dilution the  m of CH3COOH is reversible with the ion at unit concentration
increases gradually? and at 1 bar and 250C.
2) (b) E =E
0
−
0.059
log
1
Mg2+ /Mg Mg2+ /Mg 2 2+
[Mg ]
34) Assertion : Cu is less reactive than hydrogen. 0 0.059 2+
E = E 2+ + log[Mg ]
Reason :Ecell is negative. Mg2+ /Mg Mg /Mg 2

35) Assertion : ECell should have a positive value Y = C+M X

for the cell to function.
Reason : Ecathode < Eanode
36) Assertion : Conductivity of all electrolytes
decreases on dilution.
Reason : On dilution number of ions per unit
volume decreases.
37) Assertion : Λm for weak electrolytes shows a
sharp increase when the electrolytic solution is
diluted.
Reason : For weak electrolytes degree of
dissociation increases with dilution of solution.
38) Assertion : Mercury cell does not give steady
potential.
Reason : In the cell reaction, ions are not
involved in solution.
39) Assertion : Electrolysis of NaCl solution gives
chlorine at anode instead of O2.
Reason : Formation of oxygen at anode
requires overvoltage.
40) Assertion : For measuring resistance of an
ionic solution an AC source is used.
Reason : Concentration of ionic solution will
change if DC source is used.
41) Assertion : Current stops flowing when ECell =
0.
Reason : Equilibrium of the cell reaction is
attained.
42) Assertion : EAg+/Ag increases with increase in
concentration of Ag+ ions.
Reason : EAg+/Ag has a positive value.
The plot against log 2+ will be straight
[Mg ]
E 2+
Mg /Mg
line with positive slope and intercept.
3) (C) Ecell is an intensive property while G of
cell reaction is an extensive property. Intesive
property does not depend on the amount of
substance present in the system.
4) (b) Cell emf = Potential difference between the
two electrodes when no current +is drawn
through the cell.
5) (d) Inert electrodes like platinum do not
participate in electrode process however gain or
loss of electrons (redox) process takes place on
its surface.
6) (C) Electrochemical cell when recharged, act as
electrolytic cell. The condition for recharging is:
Eexternal > Ecell
7) (b) Cr (s) → Cr 3+ + 3e − Ecr0 3+ / Cr = 0.74V
Cr (s) is strongest reducing agent. Greater is the
negative value of standard reduction potential,
more is the reducing character
8) (C ) MnO −4 + 8H + + 5e − → Mn 2 + + 4H 2 O
E 0MnO − / Mn 2 + = +1.51V
4

43) Assertion : Copper sulphate can be stored in Greater is the positive value of standard
zinc vessel. reduction potential, stronger is the oxidising
Reason : Zinc is less reactive than copper agent.

45
 JMD ੴ

2+ − 3+ 0 Cu 2+ / Cu Is stronger oxidising agent than

9) (b) Mn  Cl  Cr  Cr (Lesser is the E cred ,
+
Increasing Power H / H2
2+
grater is the reducing power) Cu + 2e − → Cu (s)
10) (d) MnO −4 is stronger oxidising agent hence it Thus, copper cannot displace H2 from acids.
will give most stable ion in its reduced form. 17) (a,c) H 2 SO 4 → 2H + + SO 24−
⎯→ H + + OH −
H 2O ⎯
MnO −4 + 8H + + 5e − → Mn 2+ + 4H 2 O
( Stable )
Cathode: 2H + + 2e − → H 2

11) (a) Cr(s) is stronger oxidising agent hence it will Anode: 2H 2 O(l) → O 2 (g ) + 4H + (aq ) + 4e −

give most stable ion in its oxidized form. 18) (b,c) We know,
2.303RT
Cr (s) → Cr 3+ (aq.)+ 3e − E = E0 − log 10 Q
( stable ) nF
12) (C) Molten Al2O3 on electrolysis give aluminum
At equilibrium, E = 0, Q =K
at cathode
Given E0 = 1.1 V, n = L for Daniell cell
Cathode: Al 3+ + 3e − → Al
From eq. (i)
Anode: 2O 2− → O 2 + 4e −
2.303RT
0 = 1.1 − log10 K
I mole aluminum requires 3 mol electron i.e., 3 2F
faraday charge.
2.303RT
log10 K = 1.1
13) (a) Charging 2F
H 2 O  H + (aq ) + OH − (aq )
involves reverse 2.303 RT
log10 K
reaction to that of discharging process 2F
PbSO4 will reduce to Pb at anode.
0 0 0
19) (a,b) Conductivity depends on, nature and
14) (b)  m(NH + −
Cl) m(NaOH)
4 m(NaCl) concentration of electrolyte solution.
= [ NH + 0m Na + + 0m OH − ] − [0m Na + + 0m Cl − ]
0
m
+
4

= [0m NH +4 + 0m OH − ] =  0m NH 4 OH 20) (a , c) CuSO 4 (aq ) → Cu 2+ (aq ) + SO 24− (aq )

Cathode: Cu 2+ + 2e − → Cu
+ −
15) (d) 2H 2 O(l) → O 2 (g) + 4H (aq) + 4e Anode: 2OH − (aq) → H 2 O(l) + 1 O 2 (g) + 2e −
2
E 0cell = +1.23V (Expected reaction)
21) (a,b) When aqueous solution of CuSO4is
1
−
Cl (aq) → Cl 2 (g) + e − electrolysed using copper electrode then copper
2
is a dissolve at anode and copper is deposited at
E 0cell = +1.36 V (Actual reaction)
cathode.
Reaction (ii) takes place instead of (i)
because of over potential of O2 and high Anode: Cu(s) →Cu2++2e-
concentration of Cl- ions.
Cathode: Cu2++2e-→Cu(s)
II. Multiple Choice Answers
22) (a,c) Molar conductance of an electrolyte
16) (b,d) E 0Cu 2+
/ Cu
= +0.34 V solution depends on temperature and
concentration of electrolytes in solution.
E 0H + / H = +0.0V
2

46
 CHAPTER

4 CHEMICAL KINETICS

For any chemical reaction, there are two aspects: -

• Whether, the reaction is feasible or not which is dealt in thermodynamics and,

• If the reaction is feasible, how fast does the reaction proceed which is covered in chemical kinetics.

Chemical kinetics is the branch of physical chemistry which deals with the rate of the reactions.

Different chemical reactions occur at different rates, example: - Ionic reactions like the precipitation of
AgCl, when AgNO3 is mixed with NaCl which occurs at very instantaneous or very fast rate, while there
are other reactions like rusting of iron which takes place in very slow manner.

Rate of reactions has its own significance, like during the formation of curd, when a small amount of curd
is introduced in hot boiled milk and left out for whole night the cultivation of bacteria called lactobacillus
takes place but if we cool down the milk in a faster rate by using refrigerator, curd could not be formed as
its rate of the cultivation of lactobacillus has its own significance.

➢ RATE OF REACTION
For any reaction, rate can be expressed in the term of reactant as the rate of its disappearance or in terms of
product, the rate of its appearance.

R→P

Rate = Rate of dissapeare nce of R = Rate of Appearace of P

R −R
[R] f i
In terms of reactant: - Rate of reaction = = ,
t t −t
f i

As the concentration of reactant decreases,  R should be negative quantity put rate of reaction can’t be
t
negative.
[R]
Rate of reaction = −
t
A (-) ve sign is added to make it a positive quantity

[P] Pf − Pi
Rate of the reaction = =
t t −t
f i

[R] [P]
 Rate of reaction = − =
t t
For a complex Reaction,

aA + bB → cC + dD
1 [ A ] 1 [ B] 1 [C] 1 [ D]
Rate = − =− = =
a t b t c t d t
JMD ੴ

NOTE: During expressing the rate for any reaction, we must remember that rate can be expressed in terms
of its any reactant or product and every time rate will always be equal and rate of any reaction is always
positive. In the above expression, every change is accompanied by division of its stoichiometric coefficient
which is done in order to make the rate equal and a –ve sign is added in the rate of reactant in order to make
it a (+)ve value.

E.g. N 2 + 3H 2 → 2 NH 3

- [N2 ] 1 [H 2 ] 1 [ NH 3 ]
Rate = =− =
t 3 t 2 t

It implies that the rate of reaction is the rate of disappearance of Nitrogen is equal to the one third
disappearance of hydrogen which is equal to half the appearance of ammonia.

If the rate of change of concentration of any one of their reactants or products over a very small interval of
time where ∆ i.e., the change approaches to zero, then it can be replaced by differential (d) and the rate will
be referred as instantaneous rate of reaction. Or it can also be defined as infinitesimal change in reactant
w.r.t infinitesimal change in time.

i.e., - d[R] d[P]

Rate of reaction = =
dt dt

Units of rate reaction: -

[R ] = Mol / L = Molar

Rate = change in [R] w.r.t time

 unit of rate = Molar (time) −1 OR Mol L-1 (time) −1

➢ FACTORS AFFECTING RATE OF REACTION:-

1. Concentration or partial pressure of reactant
2. Catalyst
3. Surface area of reactant and catalyst
4. Temperature
5. Radiation

All the factors altogether or individually may alter the rate of reaction.

➢ EFFECT OF CONCENTRATION: -

The rate of a reaction is only affected by the concentration of the reactant but not on the concentration of
product.

E.g. 40 Molar (Mol L-1} of H2O2 is extremely dangerous as it decomposes explosively while a dilute
solution of almost 1 molar is not dangerous as with the decreased in its concentration, the rate of its
decomposition also decreased and it can be stored at room temperature for several months.

48
JMD ੴ

Rate law expression: For a reaction, m1A + m2B → Product

Rate α [A]a,
Rate α [B]b,
Where a & b are the order of reaction w.r.t A and B Respectively and may or may not be equal to the
stoichiometric confidents m1 and m2.

Rate α [A] a [B] b

Rate = K [A] a [ B]b (Where a+b = order of reaction)
Rate constant (K) , is the measure of the rate of reaction greater the value of K, faster the reaction will be
proceed the value of rate constant is independent to the concentration of Reactant

Any Molecule or reactant with whom the order of reaction is zero is called pseudo molecule or it can be
defined as the molecule which is necessary for the reaction but does not effect on the rate of reaction or
whose concentration is independent to the rate of reaction. Ex. Hydrolysis of ester, in which water is
necessary for the completion of reaction but as it’s taken in excess so, it behaves as pseudo molecule and
its concentration can be ignore while writing the rate law,

𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶2 𝐻5 𝑂𝐻

Rate = K[H 2 O][CH 3COOC 2 H 5 ]

It apparently looks like a second order Reaction but H2O, being a Pseudo Molecule, The reaction is a Pseudo
first order Reaction.
 Rate = K' [CH 3 COOC 2 H 5 ], where K' = K[H 2 O]

A Reaction in which the overall order is zero is called Pseudo Molecular Reaction. Ex – Formation of
H2O from H2 & O2, in which the rate of formation of H2O is independent to the concentration of H2 and O2.
Most of the Ionic and Neutralization Reactions are Pseudo Molecular Reactions.

➢ MOLECULARITY OF REACTION
It’s equal to the sum of the No. of molecules of reactants involved in the balanced stoichiometric equation
i.e. the Number of reactant molecules taking part in a single step of the reaction.

Molecularity of a reaction is only applicable for elementary reactions which takes place in one step while
not for complex reactions, Which appears to take place in one step but its mechanism includes a No. of
steps from which the slowest step is the rate determining step (RDS), in which the total molecules
participates is referred as Molecularity and the rate or order of RDS will be the overall order of the reaction.

Slowest step is the rate determining step as without its completion the whole reaction couldn’t be completed
and as it’s the slowest so, the time taken by this step will represents the complete reaction.

For example, 2 NO 2 + F2 → 2 No 2 F

49
JMD ੴ

Initially it appears to be a 3rd order reaction but it’s a complex reaction which takes place in the following
steps.

NO 2 + F2 → NO 2 F + F (Slow; RDS)

NO 2 + F2 → NO 2 F (Fast)

Rate = K [NO2] [F2]

The Reaction is bimolecular with 2nd order due to the participation of two molecules in the slowest step.

Molecularity Order of Reaction

• Total No. of reaction species i.e. Molecule, Atoms, • Sum of powers of the reacting species in the rate
ions which bring the chemical change. equation
• Non zero, Non – negative and always a whole No. • May be zero, Negative or in fractions.

• Theoretical concept • Experimental concept.

• Meant for only elementary reactions • Meant for both elementary as well as for complex
reaction.

➢ UNITS FOR RATE CONSTANT:-

r
 Rate = K [R]

Rate
 =K
[R ]

-1 −1
(Mol L )s
 =K
-1 r
(molL )

 (Mol L-1 ) 1− r , S −1 = K

For Zero Order Reactions, r = 0, K = Mol L-1 S-1

For 1st Order Reactions, r = 1, K = S-1

For 2nd Order Reactions, r = 2, K = Mol-1 L-1 S-1

For 3rd Order Reactions, r = 3, K = Mol-2 L-2 S-1

➢ CALCULATION OF RATE CONSTANT (K)

Rate constant can be calculated by the following methods:-

• Initial rate method

• Integrated rate law method
• Graphical method

50
JMD ੴ

➢ INITIAL RATE LAW METHOD: -

For many chemical reactions, the expression of rate law contains only the concentrations of reactants, while
the concentrations of products do not appear. However, for some reactions that are reversible, the
concentration of products may be part of the rate law. To simplify the rate law and avoid the complication
that might be contributed by products in reversible reactions, the measurement of rate for rate law
determination is normally done at the moment the reactants are mixed. At this point, we can also assume
that the effect of product concentration is considered negligible. Therefore, the rates that are measured are
the initial rates.

In this method, the Initial rate of a reaction is determined by varying the concentration of one of the reactants
while others are kept constant.

Example:

Experiment No. [A] (Mol L-1) [B] (Mol L-1) Rate (Mol L-1 S-1)

1 0.1 0.1 6 x 10-3

2 0.2 0.2 7.2 x 10-2

3 0.3 0.4 2.33 x 10-1

4 0.4 0.1 2.40 x 10-2

Let the Rate Law,

Rate = K [A]x [B]y, where x & y are the

Order of reaction w.r.t A and B.

For Exp. -1, 6 x 10-3 = K [0.1] x [0.1] y ……….. (i)

For Exp. -2, 7.2 x 10-2 = K [0.3] x [0.2] y ……….. (ii)

For Exp. -3, 2.88 x 10-1 = K [0.3] x [0.4] y ……….. (iii)

For Exp. -4, 2.40 x 10-2 = K [0.4] x [0.1] y ……….. (iv)

On Dividing (2) and (3) as, Concentration of A is Constant y = 2

On Dividing (1) and (4) as, Concentration of B is Constant x = 1

Rate = K [A]1 [B]2, from Exp. -1,

(6 x 10 -3 Ms −1 ) = K [0.1M] 1 [0.1M] 2

K = 6 Mol-2 L2 s-1

51
JMD ੴ

➢ DETERMINATION OF ORDER OF REACTION BY INTEGRATED RATE LAW METHOD

We already did the differential rate law equation which relates the rate in change of concentration with time
or instantaneous rate. We can integrate that rate equation and obtain the integrated rate equation that gives
a relation between directly measured experimental quantities, i.e. concentrations at different times.

ZERO ORDER REACTIONS

Zero order reaction means that the rate of the reaction is proportional to zero power of the concentration of
reactants i.e. rate is independent of the concentration of the reactant. Consider the reaction,

R (reactant) P (product)

Rate = -∂[R] (from differential rate law)

∂t
Rate = k[R]0 (from rate law, power zero shows that it’s a zero order reaction)

From above two rate equations:

-∂[R] = k[R]0
∂t
-∂[R] = k ([R]0 = 1)
∂t
-∂[R] = k∂t
On integrating both sides,
-∫∂[R] = k∫∂t
-[R] = kt + I ..… equation ① (where I = integrating constant)

At initial, concentration of reactant is maximum i.e. [R]0 and time = 0 on putting these values,
-[R]0 = k × 0 + I
-[R]0 = I ,on putting this value of I in equation ①
-[R] = kt + (-[R]0) ….. equation ②
-[R] = kt - [R]0

[R]0 - [R] = k ….equation ③

t
Comparing equation [R] = -kt + [R0] which comes by taking minus
common from equation ② With the equation of a straight line, y = mx + c,
we can plot [R] against t, and get a straight line with slope = –k with
intercept equal to [R]0.
The decomposition of gaseous ammonia on a hot platinum surface is a zero
order reaction at high pressure. In this reaction, platinum metal acts as a
catalyst. At high pressure, the metal surface gets saturated with gas
molecules. So, a further change in reaction conditions is unable to alter the

52
JMD ੴ

amount of ammonia on the surface of the catalyst making rate of the reaction independent of its
concentration.

Rate = k [NH3]0 = k

It shows that the concentration of reactant decreases with increase in time while the plot of rate vs
concentration will be a staright line parallel to the concentration axis.
Decoposition of HI on the gold surface and N2O on hot platinum surface are the other examples of zero
order reaction.

HALF LIFE PERIOD : The time required to reduce the initial concentration of the reactant to half of its
initial values is called half lifetime or period and shown by t1/2.
When [R] = [R]0/2 and t = t1/2 ,on sustituting this values in equation ③,we get
t1/2 = [R]0
2k
Thus, the half life period of zero order reaction is directly proportional to its initial concentration. Hence, a
plot of t1/2 vs [R]0 will be a straight line passing through origin with a slope of k/2.
The units of rate and rate constant for zero order reactions are same i.e. mol L-1t-1 .

FIRST ORDER REACTIONS

In this class of reactions, the rate of the reaction is proportional to the first power of the concentration of
the reactant R i.e. the arte is determined by the change of one concentration term only. For example

R (reactant) P (product)

Rate = -∂[R] (from differential rate law)

∂t

Rate = k[R] (from rate law)

From above two rate equations:
-∂[R] = k[R]
∂t
-∂[R] = k∂t
[R]
On integrating both sides,

-∫∂[R] = k∫∂t
[R]

-ln[R] = kt + I ..… Equation ① (where I = integrating constant and ln = natural log)

At initial, concentration of reactant is maximum i.e. [R]0 and time = 0 on putting these values,
-ln[R]0 = k × 0 + I
-ln[R]0 = I ,on putting this value of I in equation ①

53
JMD ੴ

-ln[R] = kt + (-ln[R]0) ….. Equation ②

-ln[R] = kt - ln[R]0
ln[R]0 - ln[R] = kt

ln[R]0 = kt
[R]
2.303log[R]0 = kt (ln = 2.303log)
[R]

2.303log[R]0 = k ….. Equation ③

t [R]

Hydrogenation of ethene is an example of first order reaction.

C2H4(g) + H2 (g) C2H6(g)
Rate = k [C2H4]
All natural and artificial radioactive decay of unstable nuclei take place by first order kinetics.
On taking minus common from equation ②, ln[R] = - kt + ln[R]0 and compare with the equation of a
straight line y = mx + c also, the equation ③, we have following graphs :

HALF LIFE PERIOD :

It shows that for a first order reaction the half life doesnot depends on the initial concentration of
reaction or independent of it.
Since the rate of constant is independent to the concentration and thus depends inversly on time, the unit of
k will be time-1 i.e.s-1 .

In many reactions, the order of reaction with respect to one of the reactants is found to be non- integral
called fractional order reactions, e.g. the reaction between hydrogen and duetrium (heavy water)
Rate = k[H2][D2]1/2

54
JMD ੴ

Sometimes,the rate of a reaction decreases as the concentration of one the component is increased called
negative order reactions ,e.g. decomposition of ozone to oxygen.
Rate = k[O3]2[O2]-1

NOTE : When the rate is shown of gaseos molecules then partial pressures replaces the concentrations

• TEMPERATURE DEPENDENCE OF THE RATE OF REACTION

In actual reacting species collide with each other to form products and on increasing the temperature kinetic
energy increases so the number of effective collisions also increases which causes the faster rate of reaction.

The temperature dependence of the rate of a chemical reaction can be

accurately explained by Arrhenius equation.

Where A= Arrhenius constant and known as

frequency factor which is related to the number of binary molecular
collisions per second per litre, Ea = activation energy, R is gas constant
and T is the absolute temperature.
The two quantities A and Ea are collectively called as Arrhenius
parameters. On taking log

55
JMD ੴ

For a reaction at T1 the rate constant is k1 while on changing its temperature from T1 to T2 the rate constant
becomes k2.

On converting it from natural log to log by multiplying it by 2.303 it becomes,

• CONCEPT OF ACTIVATION ENERGY

In order to make the collisions of reacting species effective, they must
have energy either equal or greater than threshold energy (EO , minimum
amount of energy to make the collisions effective ). Now all the reacting
species may not have that energy so we have to supply them in order to
make them effective or active this supplied energy is called as
ACTIVATION ENERGY.

In the plot it can be seen that the reacting species has to absorb certain
amount of energy (activation energy) to reach the barrier (threshold energy). At the barrier they mutually
combine to form an unstable complex compound called intermediate compound which changes into
products by releasing energy. If the amount of energy released is greater than the activation energy, the
reaction is exothermic in nature while if it is less then, it will be endothermic in nature. E.g. given in the
plot is the formation of HI which is exothermic in nature.

Activation energy = threshold energy – normal energy of reactants which they posses

All the
molecules in the reacting species do not have the same kinetic energy. Since it’s difficult to predict the
behavior of any one molecule with precision, Boltzmann and Maxwell used statistics to predict the behavior
large number of molecules. According to them, the distribution of kinetic energy may be described by
plotting the fraction of molecules (NE/NT) with a given kinetic energy E vs kinetic energy. Here NE is the
number of molecules with energy E and NT is the total number of molecules.

The peak of the curve corresponds to the most probable kinetic energy, i.e. the kinetic energy of maximum
fraction of molecules. There are decreased numbers of molecules with energies lower or higher than this
value.

56
JMD ੴ

When the temperature is raised, the maximum of the curve moves to the higher energy value and the curve
broadens out.

Increasing the temperature of the substance increases the fraction of molecules, which collide with energies
greater than Ea.. it’s clear from the diagram that in the curve at (t + 10), the area showing the fraction of
molecules having energy equal or greater than activation energy gets doubled leading to doubling the rate
of reaction.

• COLLISION THEORY OF CHEMICAL REACTION

Though the Arrhenius equation is applicable under a wide range of circumstances, collision theory, which
was developed by Max Trautz and William Lewis in 1916 , provides greater insight into the energetic and
mechanistic aspects of reactions. It is based on the kinetic theory of gases.
According to this theory, the reactant molecules are assumed to be hard spheres and reaction is postulated
to occur when molecules collide with each other.
The number of collisions per second per unit volume of the reaction mixture is known as collision frequency
(Z). Another factor that affects the rate of chemical reactions is activation energy

No reaction

More CO2 formation

For a bimolecular elementary reaction.

A+B Products

rate of reaction can be expressed as Rate = ....(1)

where ZAB represents the collision frequency of reactants, A and B and represents the fraction of
molecules with energies equal to or greater than Ea. Comparing (1) with Arrhenius equation, we can say
that A is related to collision frequency. Equation (1) predicts the value of rate constants fairly accurately
for the reactions that involve atomic species or simple molecules but for complex molecules significant
deviations are observed. The reason could be that all collisions do not lead to the formation of products.
The collisions in which molecules collide with sufficient kinetic energy (called threshold energy*) and
proper orientation, so as to facilitate breaking of bonds between reacting species and formation of new
bonds to form products are called as effective collisions. To account for effective collisions, another factor
P, called the probability or steric factor is introduced. It takes into account the fact that in a collision,
molecules must be properly oriented i.e.,

Rate =

57
JMD ੴ

Thus, in collision theory activation energy and proper orientation of the molecules together determine
the criteria for an effective collision and hence the rate of a chemical reaction.
Although collision theory has certain limitations as it considers atoms or molecules to be hard spheres and
ignores the structural aspect.

➢ EFFECT OF CATALYST
A catalyst is a substance that can alter the rate of a reaction without itself undergoing any permanent
chemical change. The action of a catalyst can be explained on the basis of intermediate complex theory.
According to which a catalyst participates in a chemical reaction by forming temporary bonds with the
reactants resulting in an intermediate complex. This has a transitory existence and decomposes to yield
products and the catalyst.
It’s believed that the catalyst provides an alternate pathway by reducing the activation energy between the
reactants and the products and hence lowering the potential energy barrier.
A small amount of catalysts can catalyze a large amount of reactions which shows their high efficient nature.
A catalyst does not alter Gibb’s free energy of a reaction it catalyzes the spontaneous reactions but does not
catalyze the non-spontaneous reactions.
It also does not alter the equilibrium as it increases both the forward as well as backward reactions at the
same extent.

58
JMD ੴ

SECTION 1 : RATE LAWS AND FACTORS AFFECTING RATE

1. How is rate law different from law of mass action?

2. What will be the Molecularity Cl 1\2Cl2
3. What is the rate of disappearance of hydrogen in the following reaction?
3H 2 + N 2 → 2 NH 3
What is the order of the reaction which has rate constant, k = 3 x 10-4L mol-1s-1?
4. For the following reaction 2A + B → C the rate of formation of C is 2.2 x 10-3 mol L -1min-1 what
d[A ]
is the value of − ?
dt
5. Why Molecularity is applicable only for elementary reactions and order is applicable for elementary
as well as complex reactions?
6. Why can we not determine the order of reaction by taking into consideration the balanced chemical
reaction?
7. For a certain reaction, the rate law is Rate = k[A][B]3/2. Can this belongs to an elementary reaction?
8. For a reaction, A + B → product, the rate law is given by , r = k[A]1/2[B]2.What is the order of the
reaction ?
9. The decomposition of dimethyl ether leads to the formation of CH4, H2 and CO and the reaction rate
is given by rate = k[CH3OCH3]3/2.The rate of reaction is followed by increase in pressure in a closed
vessel, so the rate can also be expressed in terms of the partial pressure of dimethyl ether, i.e. rate =
k(PCH3OCH3)3/2. If the pressure is measures in bar and time in minutes, then what are the units of rate
and rate constant?
10. Write the rate equation for the reaction, 2A + B → C if, the order of the reaction is zero.
11. For which type of reactions, order and molecularity have the same value?
12. For an elementary reaction 2A + B 3C

The rate of appearance of C at time (t) is 1.3 × 10-4 mol l-1 s-1.
Calculate a) rate of the reaction b) Rate of disappearance of A
Short Answer Questions

1. A reaction is second order with respect to a reactant. How is the rate of reaction affected, if the
concentration of the reactant is
(i) Doubled?
(ii) Reduced of half?
2. The conversion of molecules x to y follows second order kinetics. If concentration x is increased to
three times, how will it affect the rate of formation y?
3. A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration off B three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled?
4. The reaction, N2(g) +O2(g) ⇌ 2NO9g0 contributes to air pollution wherever a fuel is burnt in air at
a high temperature. At 1500 K, equilibrium constant K for it, is 1.0 x 10-5. Suppose in a case [N2] =
0.80 mol L-1 and [O2] = 0.20 mol L-1 before any reaction occurs. Calculate the equilibrium
concentration of the reactants and the product after the mixture has been heated to 1500 K.

59
JMD ੴ

5. The reaction between A and B is of first order with respect to A and zero order with respect to B.
fill in the blanks in the following table:
Exp. No. [A]/mol L-1 [B]/mol L-1 Initial rate/mol L-1
min-1

I 0.1 0.1 2.0 x 10-2

II - 0.2 4.0 x 10-2

III 0.4 0.4 -

IV - 0.2 2.0 x 10-2

6. In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial
concentrations of A and B as given below:
A/mol L-1 0.20 0.20 0.40

B/mol L-1 0.30 0.10 0.05

ro/mol L-1s-1 5.04 x 10-5 5.07 x 10-5 1.43 x 10-4

What is the order of the reaction with respect to A and B?

7. A reaction is of second order in A and first order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of A three times?
(iii)How is the rate affected when the concentration of both A and B is doubled?
SECTION 2 : INTEGRATED RATE LAW

Very Short Answer Questions

1. What is the order of a reaction that is 50% complete after 2 h and 75% complete after 4 h?
2. The decomposition of NH3 gas an platinum surface has a rate constant K = 2.5 × 10-4 mol l-1 s-1.
What is the order of reaction?
3. Time required to decompose SO2Cl2 to half of its initial amount is 60 min. If the decomposition is
a first order reaction, calculate the rate constant of the reaction.
4. Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law
t1/2 = 3 Hrs. calculate the fraction of sucrose which remains after 8 hrs.
Short Answer Questions

1. The thermal decomposition of HCO2H is a first order reaction with a rate constant of 2.4×10-3 S-1
at a certain temperature. Calculate how long will it take for three fourths of initial quantity of HCO2H
to decompose.
2. The decomposition of phosphine PH3 proceeds according to the reaction

4PH3 P4 + 6H2 and follows the Rate equation, Rate = K (PH3). The half-life of PH3
is 37.9 at 1200C.

60
JMD ੴ

a. How much time is required for 3\4th of PH3 to decompose?

b. What fraction of original sample of PH3 remain behind after 1 minute
3. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume.
SO 2 Cl 2 (g) → SO 2 (g ) + Cl 2 (g)
Exp. No. Time/s-1 Total pressure / atm

1. 0 0.5

2. 100 0.6

4. Consider a certain reaction

A → Products, with k=2.0 x 10-2s-1. Calculate the concentration of A remaining after 100 s if the
initial concentration of A is 1.0 mol L-1.
5. The half-life for radioactive decay of 14 C is 5730 yr. An archaeological artefact containing wood
had only 80% of the 14C found in a living tree. Calculate the age of the sample.
6. Define the following terms:
(i) Pseudo first order reaction
(ii) Half-life period of reaction (t1/2).
7. Calculate the half-life of a first order reaction from their rate constants given below;
(i) 200 s-1 (ii) 2 min-1 (iii) 4yr-1
8. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2. (Ans. 77.78 min)
9. The rate constant for a first order reaction is 60 s-1. How much time will it take to reduce the initial
concentration of the reactant to its 1/16th value? (4.62 x 10-2s)
10. The half-life of reaction is 50 minutes. What will be the order of the reaction if reaction completes
in 100 minutes?
11. A first order reaction takes 100 minutes for completion of 60% of the reaction. Find the time when
90% of reaction will be completed.
12. The rate of formation of a dimer in a second order dimerization reaction is 9.5 x 10-5 mol It-1 sec-1
at 0.01 mol It-1 monomer concentration. Calculate the rate constant.
13. The reaction 2NO+Br2 → 2NOBr2 has the mechanism.

(a) Step I NO + Br2 ↔ NOBr2 (Fast)

(b) Step II NOBr2 + NO → 2NOBr2

What will be the rate law?
14. The decomposition of NH3 on platinum surface, 2H 3 (g) ⎯⎯→
Pt
N 2 (g) + 3H 2 (g) is a zero order with
k = 2.5 x 10-4 mol L-1s-1. What are the rate of production of N2 and H2?
15. Calculate two-third life of a first order reaction having, k = 5.48 x 10-14s-1.
16. A first order gas reaction has k = 1.5 x 10-6 per second at 2000C . If the reaction is allowed to run
for 10 h what , percentage of the intial concentration would have change in the product? (5.21 %)
17. The rate constant for an isomerisation reaction A → B is 4.5 x 10-3 min-1. If the initial concentration
of A is1 M, calculate the rate of reaction after 1 h.
18. A first order reaction takes 100 min for completion of 60% of the reaction. Find the time when 90
% of the reaction will be complete?

61
JMD ੴ

19. The half-life period of a first order decomposition of nitramide is 2.1 h at 150C.
NH 2 NO 2 (aq ) → N 2 O(g ) + H 2 O(l)
If 6.2 g of NH2NO2 is allowed to decompose, calculate
(i) Time taken for NH2NO2 to decompose 99% and
(ii) Volume of dry N2O produced at this point at STP.
20. For a first order reaction, show that the time required for 99% completion is twice the time required
for the completion of 90% of reaction.
21. The half-life period of a radioactive element is 140 days. After 650 days, what amount of 1 g of
the element will be reduced? ([A] = 0.04 g)
22. Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law,
with t1/2 = 3h. What fraction of sample of sucrose remains after 8h? (0.1576 M)
23. A first order reaction has a rate constant 1.15 x 10-3s-3. How long will 5 g of this reactant take to
reduce to 3 g? (444s)
Long Answer Questions

1. For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data is
obtained:
T(s) P(mm of
Hg)

0 35.0

360 54.0

120 63.0

Calculate the arte constant.

2. During nuclear explosion, one of the products is 90Sr with half-life of 28.1 yr.If 1µ g of 90Sr was
absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after 10
yr and 60 yr if is not lost metabolically? (amount left after 10 yr = 0.7819 µg ,Amount left after 60
yr = 0.2280µg)
3. The experimental data for decomposition of N2O5, [2 N 2 O 5 → 4 NO 2 +O 2 ] in gas phase if 318 K
are given below:

t/s 10-2 x [N2O5]/mol

L-1

0 1.63

400 1.36

800 1.14

1200 0.93

62
JMD ੴ

1600 0.78

2000 0.64

2400 0.53

2800 0.43

3200 0.35

(i) Plot [N2O5] against t.

(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log [N2O5] and t.
(iv) What is the rate law?
(v) Calculate the rate constant.
(vi) Calculate the half-life period from k and compare it with (ii).

➢ NCERT EXEMPLAR

1. The rate of a chemical reaction tells us about
a. the reactants taking part in the reaction
b. the products formed in the reaction
c. how slow or fast the reaction is taking
place
d. none of the above
2. In the rate equation, when the concentration of
reactants is unity then the rate is equal to
b. The stoichiometric coefficient of the
reactants doesn’t affect the order
c. Order of reaction is the sum of power to
express the rate of reaction to the
concentration terms of the reactants.
d. Order can only be assessed
experimentally
5. The rate constant of zero-order reactions has
the unit

a. specific rate constant a. s-1

b. average rate constant b. mol L-1 s-1
c. instantaneous rate constant c. L2 mol-2 s-1
d. None of the above d. L mol-1 s-1
3. The average rate and instantaneous rate of a 6. In the reaction 2A + B → A2B, if the
reaction are equal concentration of A is doubled and that of B is
halved, then the rate of the reaction will
a. at the start
b. at the end a. increase 2 times
c. in the middle b. increase 4 times
d. when two rates have a time interval equal c. decrease 2 times
to zero d. remain the same
4. Which of the following observations is 7. when the rate of the reaction is equal to the
incorrect about the order of a reaction? rate constant, the order of the reaction is

a. Order of a reaction is always a whole a. zero order

number b. first order

63
JMD ੴ

c. second order D. The concentration of the product

d. third order
8. A substance ‘A’ decomposes by a first-order 14. On increasing the temperature the rate of
reaction starting initially with [A] = 2.00M and reaction increases mainly because
after 200min, [A] becomes 0.15M. For this A. The activation energy of the reaction
reaction t1/2 is increases
B. The concentration of the reacting molecules
a. 53.72 min increases
b. 50.49 min C. Collision frequency increases
c. 48.45 min D. None of these
d. 46.45 min
9. In the Haber process for the manufacture of 15. -d[N2O5]/dt represents
ammonia the following catalyst is used A. The rate of formation of N2O5
B. The rate of decomposition of N2O5
a. Platinized asbestos C. Order of the reaction
b. Iron with molybdenum as a promoter D. None
c. Copper oxide
d. Alumina 16. The value of activation energy is primarily
10. A catalyst alters, which of the following in a determined by
chemical reaction? A. Temperature
B. Effective collision
a. Entropy C. Concentration of reactants
b. Enthalpy D. Chemical nature of reactants and products
c. Internal energy
d. Activation energy 17. Sum of exponents of molar concentration is
11. The rate of reaction called
A. Increases as the reaction proceeds A. Order of reaction
B. Decreases as the reaction proceeds B. Molecularity
C. Remains the same as the reaction proceeds C. Rate of reaction
D. May decrease or increase as the reaction D. Average of reaction
proceeds
12. The addition of a catalyst to the reaction 18. Spontaneous reactions are
system A. Moderate
A. Increases the rate of forwarding reaction only B. Slow
B. Increases the rate of the reverse reaction C. Fast
C. Increases the rate of forwarding but decreases D. Not natural
the rate of backward reaction
D. Increases the rate of forward as well as 19. In rate expression the concentration of
backward reaction equally reactants is negative. It shows
13. The specific rate constant of a first order A. The concentration of reactant does not change
reaction depends on the B. The concentration of product increases
A. Time C. The concentration of reactant decreases
B. The concentration of the reactant D. The concentration of reactant increases
C. Temperature

64
 CHAPTER

8 d-BLOCK ELEMENTS

Electronic Configuration:
(n-1)d1-10 ns0, 1 or 2
First transition or 3d-series: This series consists of elements from Sc(21) to Zn (30). The configurations
of Cr and Cu are different than expected. The actual configurations are explained on the basis of stability
concept of half-filled or completely filled (n01) d-orbitals. (n-1) d-subshell is more stable when 5 or 10
electrons are present, i.e. every d-orbital is either singly occupied or doubly occupied.
Second transition or 4d-series: This series consists of elements from Y(39) to Cd(48).
Third transition or 5d-series: This series consists of elements from La(57) to Hg(80) except 14 elements
of lanthanide series from Ce(58) to Lu(71).
Fourth transition or 6d-series: This series consists of element from Ac (89) to Uub(11) except 14 elements
of actinide series fro Tn (90) to Lr(103).
GENERAL TRENDS
1) Metallic character:
All the transition elements are metals. They passes metallic luster, high density, high melting and boiling
points, malleability, ductility, high tensile strength, hardness, brittleness, etc. They are good conductors of
heat and electricity.
JMD ੴ

The presence of unpaired and unfilled d-orbitals favours covalent bonding. Greater the number of unpaired
d-electrons, greater number of covalent bonds and therefore, greater is the strength of these bonds. Cr, Mo
and W are very hard metals as they have maximum number of unpaired d-orbitals while Zn, Ce and Hg are
softer in nature as they do not have any unpaired d-orbitals.
2) Atomic radii:
The atomic radii of transition elements in a given series decrease with increase in atomic number but this
decrease becomes small after midway.
The decrease in atomic radii in each series, in the
beginning, is due to an increase in nuclear charge from
member to member which tends to pull the ns-electrons
inward, i.e., it tends to reduce the size. At the same time,
the addition of extra electrons to (n-l)d-orbitals also
provides the screening effect. As the number of d-electrons
increases, the screening effect increases. Thus, there are
operating two effects namely screening effect and nuclear
charge effect which oppose each other. In the midway
onwards of the series both these effects become nearly
equal and thus, there is no change in atomic radii inspite of the fact that atomic number increases gradually.
At the end of the series, there is slight increase in the atomic radii. This is due to electron-electron repulsions
among (n -l)d-electrons.
In a vertical row, i.e., in each group, the atomic radii are expected to increase from top to bottom due to the
addition of a newer shell. Therefore, the atomic radii of transition metals of second series have higher values
than those of first transition series. However, the transition metals of third series except the first member,
lanthanum, have nearly the same radii as metals of second transition series above them.
This is due to Lanthanoid contraction. Due to inclusion of fourteen elements between lanthanum and
hafnium, there is continuous decrease in size from cerium to lutetium (4f-orbitals are successively filled)
and hence, the size of hafnium becomes nearly equal to the size of zirconium.
3) Densities:
The densities of transition metals are high. Within a series, the densities increase gradually. The densities
of second series are also high (higher than first series) and of third series still higher. The two elements
osmium and iridium have highest densities 22.59 g cm-3 and 22.6L g cm-3 respectively.
4) Melting and boiling points:
The transition metals have very high melting and boiling points. In each series, the melting points of these
metals rise to a maximum value and then decrease with increase in atomic number. However, manganese
and technetium have abnormally low melting points.
The abnormal low value of manganese is probably due to stable electronic configuration (3d –all orbitals
are singly occupied, 4s2 fully filled). As the 3d-electrons are more tightly held by the nucleus the electrons
are not available for bonding resulting weaker metallic bonding in manganese in comparison to chromium.

66
JMD ੴ

Tungsten (W) has the highest melting point (3683 K) amongst transition metals.
The high melting and boiling points of transition metals are attributed to stronger forces that bind their
atoms together. The presence of one or more unpaired d-electrons contributes to higher interatomic forces
on account of covalent bonding. This is clear from their high enthalpies of atomization.
When unpaired electrons are absent, the melting points are low as in the case of Zn, Cd and Hg
5) lonization energies:
The ionisation energies increase from left to right in each series. The increase, however, is not regular.
The increase in the ionisation energy values in a given transition series is explained on the basis of
increasing nuclear charge and screening effect of (n -I)d-electrons on ns electrons. With the increase of
electrons in (n-1)d-subshell, the outer ns-electrons are shielded more. Thus, the effect of increasing nuclear
charge is somewhat neutralized by the additional screening effect and consequently, ionisation potential
increases but quite slowly among a period of d-block elements. The value of zinc is appreciably higher due
to additional stability associated with completely filled 3d-subshell in zinc.
In vertical columns, i.e., in groups, the first ionization energy decreases from first member to second
members in most of the cases as expected. However, the third member has higher value than second
member. This is due to lanthanide contraction.
6) Standard reduction potential:
In a solution, the stability of the compounds depends upon electrode potentials. Electrode potential value
depends upon enthalpy of sublimation of the metal, the ionization enthalpy and hydration enthalpy,

M(s) → M+(aq) + e– HT (Total energy change)

This process involves three steps:

First Step: M(s) → M(g) HSub (Energy of sublimation)

Second Step: M(g) → M+(g) + e– IE (Ionisation Energy)
Third Step: M+(g)+aq → M+(aq) Hhyd. (Hydration Energy)
Thus, HT = HSub.+ I.E. + Hhyd.
Element Ti V Cr Mn Fe Co Ni Cu Zn
E0( M2+ / M)V -1.63 -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 -0.34 -0.76
E0( M3+ / M2+)V -0.37 -0.26 -0.41 +1.57 +0.77 +1.97 - - -

HT is the total energy change when a solid metal, M, is brought in the aqueous medium in the form of
monovalent ion, M+ (aq).
The smaller the value of total energy change for a particular oxidation state in aqueous solution, greater will
be the stability of that oxidation state. The electrode potentials are the measure of total energy change.
Hence, quantitatively, the stability of transition metal ions in different oxidation states in a solution can be
determined on the basis of the electrode potential data. The lower the electrode potential, i.e., more negative
the standard reduction potential of the electrode, more stable is the oxidation state of the transition metal in
an aqueous medium.

67
JMD ੴ

It is evident that there is no regular trend in the E0(M2+/ M) values. This is due to irregular variation of
ionisation energies and sublimation energies of the atoms of the members of the transition series.

Except copper due to its unstable configuration of 3d9, all other elements have negative reduction potential
values, i.e., these elements except copper should have the capacity to liberate hydrogen from the dilute acids

Chromium, in spite of its high negative reduction potential value is an unreactive metal as it does not
liberate hydrogen .due to a thin coating of Cr2O3 on its surface. Copper having positive E0 value, does not
liberate hydrogen from acids.

E0 value for Sc3+/Sc2+ is very low. Hence, Sc3+ is stable. This is due to its noble gas configuration.

E0 value for M3+/ M2+ is high. This reflects that Mn2+ state is stable due to d5 configuration.

7) Oxidation states:

The transition metals with the exception of few show a large number of oxidation states. The various
oxidation states are related to the electronic configuration of their atoms.

The variable oxidation state of transition metal is due to involvement of ns and (n-1)d-electrons in bonding
as the energies of ns and (n-1)d- subshells are nearly equal.

The oxidation states of transition elements, the following conclusions are drawn:

• Generally, within the transition series, the highest oxidation state increase with increases of atomic
number, reaching to the maximum in the middle and then starts decreasing.
• In general, the minimum oxidation state shown by a transition metal is equal to the number of ns-
electrons. Except scandium, (which has + 3 Oxidation state) for the elements of first transition series,
+2 oxidation state is the most common. This state arises due to loss of 4s-electrons. However, for
chromium and copper, the lowest oxidation state is +1. This is due to their electronic configurations,
Cr(3d5 4s1)
• The maximum oxidation state shown by transition elements is the number of ns electrons and (n-
1)d electrons.
• In a group of d block elements, the higher oxidation states are more stable for heavier elements. It
means on moving down the group, the stability of higher oxidation state increases. Example in group
6 chromium is least stable in +6 oxidation state and this is why chromium is behaving like a good
oxidising agent at +6 while molybdenum and tungsten are quite stable in +6 oxidation state and that
is why they do not show any oxidising properties. Thus the stability order of their oxide is WO 3>
MoO3 >CrO3.
• Cations of the second and third-row transition metals in lower oxidation states (+2 and +3) are
much more easily oxidized than the corresponding ions of the first-row transition metals. For
example, the most stable compounds of chromium are those of Cr(III), but the corresponding
Mo(III) and W(III) compounds are highly reactive.

• On comparing to p block elements d block elements shows difference in behavior of oxidation states
as in d block on moving down the group the stability of higher oxidation state increases while in p
block the stability of higher oxidation state decreases down the group due to inert pair effect.

68
JMD ੴ

• Also, in d block, elements shows successive oxidation states while in p block elements shows
alternative oxidation states means successive oxidation states differ by 1.
• Some of the transition metals form compounds in zero oxidation state. The common examples are
Ni(CO)4 and Fe(CO)5 in which nickel and iron-are in zerovalent state.
• In +2 and +3 oxidation states, the bonds formed are mostly ionic. On the other hand, in higher
oxidation states, the bonds formed are essentially covalent. Higher states are usually attained with
elements of high electronegativity such as fluorine and oxygen:
• The relative stability of various oxidation states of a given element can be explained on the basis of
stability of d0, d5 and d10 configurations.
• Cations of the second and third-row transition metals in lower oxidation states (+2 and +3) are
much more easily oxidized than the corresponding ions of the first-row transition metals. For
example, the most stable compounds of chromium are those of Cr(III), but the corresponding
Mo(III) and W(III) compounds are highly reactive.

8) Coloured compounds:

0
NOTE : Potassium permanganate and Potassium dichromate are coloured though they have d
configuration due to their ligand-metal charge transfer (LMCT)

69
JMD ੴ

9) Magnetic properties:

These are either paramagnetic or diamagnetic. A paramagnetic substance is one which is weakly attracted
into a magnetic field and a diamagnetic substance is one which is repelled by a magnetic field. The
paramagnetic behavior arises due to the presence of one or more singly occupied atomic orbitals while
diamagnetic be behavior is due to presence of paired electrons in the atomic orbitals.

Most of the compounds of transition elements are paramagnetic in nature as unpaired electrons in d-subshell
are present. The magnetic character is expressed in terms of magnetic moments.

𝜇𝑒𝑓𝑓 = √𝑛(𝑛 + 1)𝐵. 𝑀.

10) Tendency to form complexes:

d-block elements have a marked ability to form complex compounds. This ability is on account of following
three reasons:

(i) Small size

(ii) high nuclear charge
(iii) a number of vacant of equivalent energy where the electrons donated by ligands can be
accommodated.

The numbers of attachments with ligands are usually either four or six, i. e., the coordination number of
metal ion is usually four or six. The compounds containing complex ions are termed as coordination
compounds.

11) Formation of interstitial compounds:

Small non-metallic atoms such as H, B, C, N, etc., are able to occupy interstitial spaces of the lattices of the
d-block elements to form combinations which are termed interstitial compounds. They are usually non-
stoichiometric materials having formulae like TiC, Mn4, N Fe3 H, VH0.56, TiH1.7, etc., The bonds present in
them are neither typically ionic nor covalent.

(i) The interstitial compounds have similar chemical properties as the parent metals but differ
appreciably in their physical properties such as density, conductivity, etc.

(ii) As a result of filling up of the interstitial spaces, the metals become rigid and hard. Steel is quite
hard as it is an interstitial Compound of Fe and C. Some of the borides are as hard as diamond.

(iii) Interstitial compounds possess high melting points which are higher than those of pure metals.

12) Catalytic properties:

Many of the l-block elements and their compounds act as catalysts in various reactions. Some common
examples are:

(i) Ft-used as a catalyst in the manufacture of H2SO4.

(ii) Fe-used as a catalyst in the manufacture of NH3 by Haber process. A small amount of
molybdenum is added as a promoter.

70
JMD ੴ

(iii) Ni-used as a catalyst in the hydrogenation of oils.

(iv) V2O5-used as a catalyst for the oxidation of SO2 into SO3.

(v) MnO2-used as a catalyst in the decomposition of KCIO3 for preparation of oxygen.

(vi) Cobalt salts

The catalytic activity of transition metals is attributed to the following reasons:

(i) Because of their variable valencies, transition metals form unstable intermediate compounds and provide
a new path with lower activation energy for the reaction.

(ii) Transition metals provide a suitable surface where the reactants are adsorbed and thus come closer to
one another facilitating the reaction to proceed.

13) Alloy formation:

Transition metals form a large number of alloys. Since d-block elements are quite similar in atomic size,
the atoms of one metal can substitute the atoms of other metal in its crystal lattice. Thus, on cooling a
mixture solution of two or more transition metals, smooth solid alloys are formed, Alloys are generally
harder, stronger, have desirable casting properties, have high melting points and are more resistant to
corrosion than the individual metals.

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JMD ੴ

COMPOUNDS OF d BLOCK

Potassium Dichromate, K2Cr2O7:

It is the most important compound of chromium. The potassium dichromate is mainly used in the
production of potassium chrome alum, and in the leather tanning industry.It is manufactured from
chromite ore (FeO. Cr2 O3) which is a mixed ore. The manufacture of potassium dichromate involves the
following steps:

1. Conversion of chromite into sodium chromate:

4FeO. Cr2 O3 + 8Na2CO3 + 7O2 → 8Na2CO4 + 2Fe2O3 + 8CO2

2. Conversion of sodium chromate into sodium dichromate:

2Na2CrO4 +H2SO4 → Na2Cr2O7 + Na2SO4 + H2O

3. Conversion of sodium dichromate into potassium dichromate:

Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

Na2Cr2O7 is deliquescent enough and changes its concentration and cannot be taken as primary standard
solution whereas K2Cr2O7 has no water of crystallisation and is not deliquescent.

Properties :

(i) It is an orange red crystalline compound. It is moderately soluble in cold water but freely soluble in
hot water.

(ii) On heating strongly, it decomposes liberating oxygen.

4K2Cr2O7 → 4K2CrO4 + 2Cr2O3 + 3O2

(iii) On heating with alkalies, it is converted to chromate, i.e., colour changes from orange to yellow. On
acidifying the yellow colour again changes to orange.

2− 2−
Cr2O + 2OH– → 2CrO + H2O
7 4
Orange
2− 2−
2Cr2O + 2H+ → Cr2O + H2O
4 7
Yellow

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JMD ੴ

i. e., in alkaline solution, chromate ions are present while in acidic solution, dichromate ions are present'
both the ions are in equilibrium at pH = 4.

At, PH=4 .

2− 2−
2Cr2O + H 2O ⇌ 2Cr2O + 2H+
7 4
(iv) It acts as a powerful oxidising agent in acidic medium

2−
2Cr2O + 14H+ +6e– → 2Cr3+ + 2H2O
7
Some of the oxidizing reactions of K2 Cr2 O7 are given below:

(a) Iodine is liberated from potassium iodide.

K2Cr2O7 → 4H2SO4 + K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

[3KI + H2SO4 + [O] → K2SO4 + I2 + 4H2O] x 3

K2Cr2O7 + 6KI + 7H2SO4 → 4K2SO4 + Cr2 (SO4)3 + 7H2O + 3I2

(b) Ferrous salts are oxidized to ferric salts.

K2Cr2O7 → 6FeSO4 + 2H2SO4 → 3Fe2(SO4)3 + Cr2(SO4)3 + 7H2O + K2SO4

(c) Sulphites are oxidized to sulphates.

K2Cr2O7 → 3Na2SO4 + 4H2SO4 → 3Na2SO4 + K2SO4 + Cr2(SO4)3 + 4H2O

(d) H2S is oxidized to sulphur.

K2Cr2O7 → 4H2SO4 + 3H2S → K2SO4 + Cr2(SO4)3 + 7H2O + 3S

(e) SO2 is oxidized to H2SO4.

K2Cr2O7 → H2SO4 + 3SO2 → K2SO4 + Cr2(SO4)3 + 7H2O

Potassium Permanganate, KMnO4

This is the most important and well known compound of manganese. It is prepared from the pyrousite
dioxide mineral (MnO2). The preparation involves two steps:

2MnO2 + 4KOH + O2 → 2K2 MnO4 + 2H2O

Oxidation of potassium manganate to potassium permanganate:

2K2 MnO4 + Cl2 → 2KMnO4 + 2KCI

Properties:

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JMD ੴ

(i) It is a purple coloured crystalline compound. It is fairly soluble in cold water and hot water. The
solubility in hot water is, however, more. It melts at 2500C.

(ii) When heated strongly, it decomposes evolving oxygen.

2K2 MnO4 → K2MnO4 + MnO4 + O2

Potassium permanaganate acts as an oxidizing agent in alkaline, neutral or acidic solutions.

(a) In alkaline solution:

𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑒
2KMnO4 + H2O → 2MnO2 + 2KOH + 3[O]

2MnO4̅ + H2O → 2MnO2 + 2OH– + 3[O]

(b) In neutral solution:

2KMnO4 + H2O → 2MnO2 + 2KOH + 3[O]

2MnO4̅ + H2O → 2MnO2 + 2OH– + 3[O]

(c) In acidic solution (in presence of dilute H2SO4) :

2KMnO4 + 3H2SO4 → K2SO2 + 2MnO4 + 3H2O + 5[O]

Examples:-

(i) Ferrous salts are oxidised to ferric salts,

2KMnO4 + 10FeSO4 + 8H2SO4 → 5Fe2(SO4)3 + K2SO4 2MnSO4 + 8H2O

(ii) Iodine is evolved from potassium iodide.

2KMnSO4 + 10KI + 8H2SO4 → 6K2SO4 + 2MnSO4 + 5I2 + 8H2O

(iii) H2S is oxidised to sulphur.

2KMnSO4 + 3H2SO4 + 10H2SO4 → K2SO4 + 2MnSO4 + 5S

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JMD ੴ

In Acidic Medium:

(i) Ferrous salts are oxidised to ferric salts.

(ii) Potassium iodide is converted to iodine.

(iii) H2S is oxidised to sulphur.

(iv) SO2 is oxidised to H2SO4.

(v) Nitrites are oxidised to nitrates.

(vi) Oxalic acid is oxidised to CO2.

(vii) Hydrogen halides (HCI, HBr or HI) are oxidized into X2(halogen).

In Neutral Medium:

(i) H2S is oxidised to sulphur.

(ii) Manganese sulphate is oxidised to MnO2

(iii) Sodium thiosuiphate is oxidised to sulphate and sulphur.

In Alkaline Medium

(i) Iodide is oxidized to iodate.

(ii) Ethylene is oxidized to ethylene glycol.

In alkaline medium it is called Baeyer’s reagent.

Uses of Potassium Permanganate

i) Oxidizing agent in laboratory & industry.

ii) in volumetric analysis − as intermediate solution generally.

iii) As Bayer’s reagent in organic chemistry for test of unsaturation the products being colourless, the
decolourisation of pink colour of the reagent takes place.

iv) In qualitative analysis for detection of a halides sulphites, oxalates etc.

v) Bleaching of wool, cotton, silk and other textiles.

vi) Decolourization of oils

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JMD ੴ

LANTHANIDES

Lanthanides consist of elements that follow lanthanum and involve the filling of 4f subshell

Electronic Configuration [Xe] 4f1-14 5dO-1 6s2

Atomic and Ionic Sizes of Lanthanides

Atomic and ionic radii of lanthanides decrease with an increase in atomic number. This gradual
decrease is known as lanthanides contraction.

Oxidation States of Lanthanides

Lanthanides exhibit the oxidation state of +3. Some of them also exhibit the oxidation state of +2
and +4.
Ce4+, Cerium is the only element which shows +4 oxidation state due to its a noble gas configuration
but in order to achieve its group common oxidation state, it undergoes quick reduction. That means
addition of electron that is why it is considered as a good oxidising agent.
Europium and Ytterbium both shows +2 oxidation state due to half filled stability and full filled
stability respectively and in order to achieve their group common oxidation state of +3 they undergoes
quick oxidation and behaves as a good reducing agent

Lanthanide contraction

It is observed that in lanthanide series, there is a progressive decrease in the atomic and ionic radii with
increasing atomic number. This regular decrease with increase in atomic number is called lanthanide

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JMD ੴ

contraction. This is due to the weak shielding of f-orbitals. These f orbitals are unable to counter balance
the effect of increasing nuclear charge because of which the size keeps on decreasing with increase in
atomic number.

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Consequence of Lanthanide Contraction

• Separation of Lanthanides: Without lanthanide contraction all the lanthanides would have same
size because of which if would have been very difficult to separate them but due to lanthanide
contraction their properties slightly vary. The variation in the properties is utilized for separating
them.
• Basic Strength of Hydroxide: Because of the lanthanide contraction, size of M3+ ions decreases
and there is increase in covalent character in M—OH and hence basic character decreases.
Similarity of 2nd and 3rd transition series i.e. 3d and 4 d series: The atomic sizes of second row
transition elements and third row transition elements are almost similar. This is also an effect of
lanthanide contraction. As we move down the from form 4d to 5d series, the size must increase but
it remains almost same due to the fact that the 4f electrons present in the 5d elements show poor
shielding effect.

Chemical Behaviour

The first few members of the series are quite reactive like
calcium. However with increasing atomic number, their
behaviour becomes similar to that of aluminum.

Lanthanides combine with hydrogen on gentle heating.

When they are heated with carbon result in formation of
carbides On burning in the presence of halogens,
lanthanides form halides.

Lanthanides react with dilute acids to liberate hydrogen gas.

Lanthanides form oxides and hydroxides of the type M(OH)3
which are basic alkaline earth metal oxides and hydroxides.

Uses of Lanthanides

Lanthanide are used in the production of alloy steels for plates and pipes. Mixed oxides of lanthanides are
used as catalysts in petroleum cracking industries.

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JMD ੴ

Some lanthanum oxides are used as phosphors in television screens and other fluorescing surfaces.
Used in making alloy Mischmetal . It is also called cerium mischmetal, or rare-earth mischmetal. it
contains 95% lanthanides and 5% iron. Its most common use is in the "flint" ignition device of
many lighters and torches

ACTINIDES

Actinides consist of elements that follow actinium and involve the filling of 5f subshell . All the actinides
are radioactive in nature. Radioactivity increases with increase in atomic number. Due to their
radioactivity and variability in oxidation states chemistry of actinides are more complex than lanthanides.

Oxidation States
The dominant oxidation state of these elements is +3 (similar to lanthanides). Besides +3 state, they
also exhibit +4 oxidation state. Some actinides show still higher oxidation states. Actinides shows
variable. Oxidation states due to their comparable energies of 7s 6d and 5f

Ionization enthalpies
The actinides have lower ionization enthalpies as comapre to lanthanides because 5f is more effectively
shielded from nuclear charge than 4f.

Magnetic behavior
All actinides are paramagnetic in nature. The paramagnetic nature which depends on the presence of
unpaired electrons.

Chemical Behaviour
They react with boiling water to give a mixture of oxide and hydride.
The combine with most of the non - metals at moderate temperature.

Some Applications of d- and f-Block Elements

• Iron and steel are prime construction materials. Their production is based on the reduction of iron
oxides, the removal of impurities.
• TiO is manufactured for the pigment industry and MnO2 is manufactured for use in dry battery
cells.
• The battery industry also requires Zn and Ni/Cd.
• The 'silver' UK coins are a Cu/Ni alloy.
• Many of the metals and/or their compounds are essential catalysts in the chemical industry
o V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.
o TiCl4 with Al(CH3)3 forms the basis of the Ziegler catalysts used to manufacture
polyethylene.
o Iron catalysts are used in the Haber process for the production of ammonia from N2/H2
mixtures.
o Nickel catalysts enable the hydrogenation of fats to proceed.
• The photographic industry relies on the special light-sensitive properties of AgBr.

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JMD ੴ

PRACTICE QUESTIONS

1. On what ground can you say that scandium is a transition metal but zinc is not?
2. Cu atom has completely filled d-orbital in its ground state. How can you say that it is a transition
element?
3. Why do the transition elements exhibit higher enthalpies of atomization?
4. Why does Mn(II) shows maximum paramagnetic character amongst the bivalent ions of the first
transition series?
5. Which one of Fe2+ and Fe3+ ions is more paramagnetic and why? Explain.
6. Which of the following ions are expected to be coloured and why? Explain
7. Transition metals of 3d-seies do not react readily with dilute acids to liberate hydrogen although
they have high negative reduction potential values. Explain.
8. The second and third members in each group of the transition elements have similar atomic radii.
Explain. Or
Zr and Hf have almost identical radii. Explain.
9. Most of the compounds of transition elements are coloured. Account for this.
10. Transition metals and their compounds acts as catalysts. Explain.
11. Chromium is a typical hard metal while mercury is a liquid. Explain.
12. Why are the ionisation energies of 5d elements greater than 3d elements?
13. The melting and boiling point of Zn, Cd and Hg are low. Why
14. Why K2Cr2O7 is preferred over Na2Cr2O7 in volumetric analysis?
15. Chemistry of all the lanthanoids is quite similar. Explain giving reason.
16. Name the member of the lanthnide series which is well known to exhibit +4 oxidation state. Cerium
(Z = 58).
17. Why Ce4+ in an aqueous solution is a good oxidising agent?
18. Transition elements have high enthalpy of hydration. Explain.
19. Why do transition elements show variable oxidation states?
20. Which out of V (IV) and V (V) is paramagnetic and why?
21. Explain why CuSO4 is blue while ZnSO4 is colourless?
22. What are alloys? Name an important alloy which contains some of the lanthanoid metals. Mention
its uses.
23. What are inner transition elements? Decide which of the following atomic numbers are the atomic
numbers of the inner transition elements: 29, 59, 74, 95, 102, 104.
24. Use Hund’s rule to derive the electronic configuration of Ce2+ ion, and calculate its magnetic
moment on the basis of ‘spin-only’ formula.
25. Name the members of the lanthanoid series which exhibit +4 oxidation states and those which
exhibit +2 oxidation state. Try to correlate this type of behaviour with the electronic configuration
of these elements.
26. Write the electronic configurations of the elements with atomic numbers 61, 91, 101 and 109.
27. Compare the general characteristics of the first series of transition metals with those of the second
and third series metals in the respective vertical columns. Give special emphasis on the following
points: (i) electronic configurations, (ii) oxidation states, (iii) ionization enthalpies and (iv) atomic
sizes.

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JMD ੴ

28. Write down the number of 3d electrons in each of the following ions:
i. Ti2+, V2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+ , Ni2+ and Cu2+
b. Indicate how would you expect the five 3d orbitals to be occupied for these hydrated ions
(octahedral).
29. Comment on the statement that elements of the first transition series posses many properties
different from those of heavier transition elements.
30. State reasons for the following:
a. Cu(I) ion is not stable in an aqueous solution.
b. Unlike Cr3+ , Mn2+ , Fe3+ and the subsequent other M2+ ions of the 3d series of elements, the
4d and the 5d series metals generally do not form stable cationic species.
31. How would you account for the following:
a. Cr2+ is reducing in nature while with the same d-orbital configuration (d4) Mn3+ is an
oxidising occurs in the middle of the series.
b. In a transition series of metals, the metal which exhibits the greatest of oxidation states
occurs in the middle of the series.
32. Explain the following observations:
a. Generally there is an increase in density of elements from titanium (Z = 22) to copper (Z =
29) in the first series of transition elements.
b. Transition elements and their compounds are generally found to be good catalysts in
chemical reactions.
33. Compare the relative stability of +2 oxidation states in aqueous solutions for the metals having in
their atoms the outer electron configuration, 3d3 4s2, 3d6 4s2 and 3d5 4s2.
34. The sum of first and second ionization enthalpies and third and fourth ionization enthalpies of nickel
and platinum are:
1. IE1 + IE2 (M j mol-1) IE3 + IE4 (M j mol-1)
b. Ni 2.49 8.80
c. Pt 2.66 6.70
d. Based on the above information, answer the following:
35. Why Eo values for Mn, Ni and Zn are more negative than expected?
36. Transition metals show high melting points. Why?
37. When Cu2+ is treated with KI, a white precipitate is formed. Explain the reaction with the help of
chemical equation.
38. Out of Cu2Cl2 and CuCl2, which is more stable and why?
39. Although fluorine is more electronegative than oxygen, but the ability of oxygen to stabilize higher
oxidation states exceeds that of fluorine. Why?
40. Although Cr3+ and Co2+ ions have the same number of unpaired electrons but the magnetic moment
of Cr3+ is 3.87 B.M. and that of Co2+ is 4.87 B.M. Why?
41. Although Zr belongs to 4d and Hf belongs to 5d transition series, but it is quite difficult to separate
them. Why?
42. Although +3 oxidation state is the characteristic oxidation state of lanthanoids but cerium shows +4
oxidation state also. Why?
43. Explain why does the colour of KMnO4 disappear when oxalic acid is added to its solution in acidic
medium.

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 JMD ੴ

➢ NCERT EXEMPLAR

1. There are 14 elements in actinoid series. Which (ii) 3.87 B.M.

of the following elements does not belong to this (iii) 3.47 B.M.
series? (iv) 3.57 B.M.
(i) U 7. KMnO4 acts as an oxidising agent in alkaline
(ii) Np medium. When alkaline KMnO4 is treated with
(iii) Tm KI, iodide ion is oxidised to
(iv) Fm (i) I2
(ii) IO–
2. KMnO4 acts as an oxidising agent in acidic
(iii) IO3–
medium. The number of moles of KMnO4 that
(iv) IO4–
will be needed to react with one mole of sulphide
8. Which of the following statements is not correct?
ions in acidic solution is
(i) Copper liberates hydrogen from acids.
(i) 2 / 5
(ii) In its higher oxidation states, manganese
(ii) 3 / 5
forms stable compounds with oxygen and
(iii) 4 / 5
fluorine.
(iv) 1 / 5
(iii) Mn3+ and Co3+ are oxidising agents in
3. Which of the following is amphoteric oxide?
aqueous solution.
Mn2O7, CrO3, Cr2O3, CrO, V2O5, V2O4
(iv) Ti2+ and Cr2+ are reducing agents in aqueous
(i) V2O5, Cr2O3
solution
(ii) Mn2O7, CrO3
9. When acidified K2Cr2O7 solution is added to
(iii) CrO, V2O5
Sn2+ salts then Sn2+ changes to
(iv) V2O5, V2O4
(i) Sn
4. Gadolinium belongs to 4f series. It’s atomic
(ii) Sn3+
number is 64. Which of the following is the
(iii) Sn4+
correct electronic configuration of gadolinium?
(iv) Sn+
(i) [Xe] 4f75d16s2
10. Highest oxidation state of manganese in fluoride
(ii) [Xe] 4f65d26s2
is +4 (MnF4) but highest oxidation state in
(iii) [Xe] 4f86d2
(iv) [Xe] 4f95s1 oxides is +7 (Mn2O7) because
(i) fluorine is more electronegative than oxygen.
5. Interstitial compounds are formed when small
(ii) fluorine does not possess d-orbitals.
atoms are trapped inside the crystal lattice of
(iii) fluorine stabilises lower oxidation state.
metals. Which of the following is not the
(iv) in covalent compounds fluorine can form
characteristic property of interstitial compounds?
single bond only while oxygen forms double
(i) They have high melting points in comparison
bond.
to pure metals.|
11. Although Zirconium belongs to 4d transition
(ii) They are very hard.
series and Hafnium to 5d transition series even
(iii) They retain metallic conductivity.
then they show similar physical and chemical
(iv) They are chemically very reactive.
properties because___________. .
6. The magnetic moment is associated with its spin (i) both belong to d-block.
angular momentum and orbital angular (ii) both have same number of electrons.|
momentum. Spin only magnetic moment value (iii) both have similar atomic radius.
of Cr3+ ion is
(i) 2.87 B.M.

81
 JMD ੴ

(iv) both belong to the same group of the (iv) Lower oxidation states of heavier members
periodic table of group-6 of transition series are more stable.
25. Which of the following actinides show oxidation
12. Why is HCl not used to make the medium acidic
states upto +7?
in oxidation reactions of KMnO4 in acidic
(i) Am
medium?
(ii) Pu
(i) Both HCl and KMnO4 act as oxidising agents.
(iii) U
(ii) KMnO4 oxidises HCl into Cl2 which is also
(iv) Np
an oxidising agent.
(iii) KMnO4 is a weaker oxidising agent than 26. General electronic configuration of actinides is
HCl. (n–2)f1–14 (n-1)d0-2ns2.Which of the following
(iv) KMnO4 acts as a reducing agent in the actinides have one electron in 6d orbital?
presence of HCl. (i) U (Atomic no. 92)
(ii) Np (Atomic no.93)
Multiple Choice Questions (Type-II) (iii) Pu (Atomic no. 94)
Note : In the following questions two or more (iv) Am (Atomic no. 95)
options may be correct. 27. Which of the following lanthanoids show +2
22. Generally transition elements and their salts are oxidation state besides the characteristic
coloured due to the presence of unpaired oxidation state +3 of lanthanoids?
electrons in metal ions. Which of the following (i) Ce
compounds are coloured? (ii) Eu
(i) KMnO4 (iii) Yb
(ii) Ce (SO4)2 (iv) Ho
(iii) TiCl4 28. Which of the following ions show higher spin
(iv) Cu2Cl2 only magnetic moment value?
23. Transition elements show magnetic moment due (i) Ti3+
to spin and orbital motion of electrons. Which of (ii) Mn2+
the following metallic ions have almost same (iii) Fe2+
spin only magnetic moment? (iv) Co3+
(i) Co2+ 29. Transition elements form binary compounds
(ii) Cr2+ with halogens. Which of the following elements
(iii) Mn2+ will form MF3 type compounds?
(iv) Cr3+ (i) Cr
24. In the form of dichromate, Cr (VI) is a strong (ii) Co
oxidising agent in acidic medium but Mo (VI) in (iii) Cu
MoO3 and W (VI) in WO3 are not because (iv) Ni
___________. 30. Which of the following will not act as oxidising
(i) Cr (VI) is more stable than Mo(VI) and agents?
W(VI). (i) CrO3
(ii) Mo(VI) and W(VI) are more stable than (ii) MoO3
Cr(VI). (iii) WO3
(iii) Higher oxidation states of heavier members (iv) CrO42–
of group-6 of transition series are more stable. 31. Although +3 is the characteristic oxidation state
for lanthanides but cerium also shows +4

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 JMD ੴ

oxidation state because ___________. 44. Explain why does colour of KMnO4 disappear
(i) it has variable ionisation enthalpy when oxalic acid is added to its solution in acidic
(ii) it has a tendency to attain noble gas medium.
configuration 45. When orange solution containing Cr2O72– ion is
(iii) it has a tendency to attain f0 configuration treated with an alkali, a yellow solution is
(iv) it resembles Pb4+ formed and when H+ ions are added to yellow
solution, an orange solution is obtained. Explain
Short Answer Type Questions why does this happen?
32. Why does copper not replace hydrogen from 46. A solution of KMnO4 on reduction yields either
acids? a colourless solution or a brown precipitate or a
green solution depending on pH of the solution.
33. Why E⊖ values for Mn, Ni and Zn are more
What different stages of the reduction do these
negative than expected?
represent and how are they carried out?
34. Why first ionisation enthalpy of Cr is lower than
47. The second and third rows of transition elements
that of Zn ?
resemble each other much more than they
35. Transition elements show high melting points. resemble the first row. Explain why?
Why?
48. E⊖ of Cu is + 0.34V while that of Zn is – 0.76V.
2+
36. When Cu ion is treated with KI, a white Explain.
precipitate is formed. Explain the reaction with 49. The halides of transition elements become more
the help of chemical equation. covalent with increasing oxidation state of the
37. Out of Cu2Cl2 and CuCl2, which is more stable metal. Why?
and why?
50. While filling up of electrons in the atomic
38. When a brown compound of manganese (A) is
orbitals, the 4s orbital is filled before the 3d
treated with HCl it gives a gas (B). The gas taken
orbital but reverse happens during the ionisation
in excess, reacts with NH3 to give an explosive
of the atom. Explain why?
compound (C). Identify compounds A, B and C.
39. Although fluorine is more electronegative than 51. Reactivity of transition elements decreases
oxygen, but the ability of oxygen to stabilise almost regularly from Sc to Cu. Explain.
higher oxidation states exceeds that of fluorine.
Matching Type Questions
Why?
Note : Match the items of Column I and
40. Although Cr3+ and Co2+ ions have same number
Column II in the following questions
of unpaired electrons but the magnetic moment
52. Match the catalysts given in Column I with the
of Cr3+ is 3.87 B.M. and that of Co2+ is 4.87
processes given in Column II.
B.M. Why?
41. Ionisation enthalpies of Ce, Pr and Nd are higher
than Th, Pa and U. Why?
42. Although Zr belongs to 4d and Hf belongs to 5d
transition series but it is quite difficult to
separate them. Why?
43. Although +3 oxidation states is the characteristic
oxidation state of lanthanides but cerium shows
+4 oxidation state also. Why?

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 JMD ੴ

53. Match the compounds/elements given in Column 57. Match the property given in Column I with the
I with uses given in Column II. element given in Column II.

54. Match the properties given in Column I with the

metals given in Column II.

58. Match the properties given in Column I with the

metals given in Column II.

55. Match the statements given in Column I with the

oxidation states given in Column II.

Assertion and Reason Type Questions

Note : In the following questions a statement
of assertion followed by a statement of reason
is given. Choose the correct answer out of the
following choices.
56. Match the solutions given in Column I and the
(i) Both assertion and reason are true, and reason
colours given in Column II.
is the correct explanation of the assertion.
(ii) Both assertion and reason are true but reason
is not the correct explanation of assertion.
(iii) Assertion is not true but reason is true.
(iv) Both assertion and reason are false.

59. Assertion : Cu2+ iodide is not known.

Reason : Cu2+ oxidises I– to iodine.
60. Assertion : Separation of Zr and Hf is difficult.
Reason : Because Zr and Hf lie in the same
group of the periodic table.
61. Assertion : Actinides form relatively less stable
complexes as compared to lanthanoids.
Reason : Actinides can utilise their 5f orbitals
along with 6d orbitals in bonding but lanthanoids
do not use their 4f orbital for bonding.

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 JMD ੴ
62. Assertion : Cu cannot liberate hydrogen from
acids.
Reason : Because it has positive electrode
potential.
63. Assertion : The highest oxidation state of
osmium is +8.
Reason : Osmium is a 5d-block element
Long Answer Type Questions
64. Identify A to E and also explain the reactions
involved.
65. When a chromite ore (A) is fused with sodium
carbonate in free excess of air and the product is
dissolved in water, a yellow solution of
compound (B) is obtained. After treatment of
this yellow solution with sulphuric acid,
compound (C) can be crystallised from the
solution. When compound (C) is treated with
KCl, orange crystals of compound (D) crystallise
out. Identify A to D and also explain the
reactions.
66. When an oxide of manganese (A) is fused with
KOH in the presence of an oxidising agent and
dissolved in water, it gives a dark green solution
of
compound (B). Compound (B) disproportionates
in neutral or acidic solution to give purple
compound (C). An alkaline solution of
compound (C) oxidises potassium iodide
solution to a compound (D) and compound (A) is
also formed. Identify compounds A to D and
also explain the reactions involved.
67. On the basis of Lanthanoid contraction, explain
the following :
(i) Nature of bonding in La2O3 and Lu2O3.
(ii) Trends in the stability of oxo salts of
lanthanides from La to Lu.
(iii) Stability of the complexes of lanthanides.
(iv) Radii of 4d and 5d block elements.
(v) Trends in acidic character of lanthanide
oxides.
68. (a) Answer the following questions :
(i) Which element of the first transition series
has highest second ionisation enthalpy?
(ii) Which element of the first transition series
has highest third ionisation enthalpy?
(iii) Which element of the first transition series
has lowest enthalpy of atomisation?
(b) Identify the metal and justify your answer.
(i) Carbonyl M (CO)5
(ii) MO3F
69. Mention the type of compounds formed when
small atoms like H, C and N get trapped inside
the crystal lattice of transition metals. Also give
physical and Chemical characteristics of these
compounds.
70. (a) Transition metals can act as catalysts because
these can change their oxidation state. How does
Fe(III) catalyse the reaction between iodide and
persulphate ions?
(b) Mention any three processes where transition
metals act as catalysts.
71. A violet compound of manganese (A)
decomposes on heating to liberate oxygen and
compounds (B) and (C) of manganese are
formed. Compound (C) reacts with KOH in the
presence of potassium nitrate to give compound
(B). On heating compound (C) with conc.
H2SO4 and NaCl, chlorine gas is liberated and a
compound (D) of manganese along with other
products is formed. Identify compounds A to D
and also explain the reactions involved.
Answers to Multiple Choice Questions
I. Multiple Choice Questions (Type-I)
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1. (ii) 2. (i) 3. (iv) 4. (ii) 5. (i) 6. (ii) 7. (ii) 8. (i)
9. (iv) 10. (iii) 11. (i) 12. (i) 13. (i) 14. (iv) 15.
(ii) 16. (iii) 17. (i) 18. (iii) 19. (iv) 20. (iii) 21.
(ii)
II. Multiple Choice Questions (Type-II)
22. (i), (ii) 23. (i), (iv) 24. (ii), (iii) 25. (ii), (iv)
26. (i), (ii) 27. (ii), (iii) 28. (ii), (iii) 29. (i), (ii)
30. (ii), (iii) 31. (ii), (iii)
III. Short Answer Type
32. Cu shows positive E0 value.
33. Negative E0 values for Mn2+ and Zn2+ are
related to stabilities of half-filled and fully filled
configuration respectively. But for Ni2+ , E0
value is related to the highest negative enthalpy
of hydration.
34. Ionisation enthalpy of Cr is lower due to
stability of d 5 and the value for Zn is higher
because its electron comes out from 4s orbital.
35. The high melting points of transition metals
are attributed to the involvement of greater
number of electrons in the interatomic metallic
bonding from (n-1) d-orbitals in addition to ns
electrons
36. Cu2+ gets reduced to Cu+
2Cu2+ + 4I – → Cu2 I 2 + I2
(white precipitate)
37. CuCl2 is more stable than Cu2Cl2 . The
stability of Cu2+ (aq.) rather than Cu+ (aq.) is due
to the much more negative ∆H0hyd of Cu2+ (aq.)
than Cu+ (aq.).
38. A = MnO2 ,B = Cl2 ,C = NCl3
MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O
NH3 + 3Cl2 → NCl3 + 3HCl
39. It is due to the ability of oxygen to form
multiple bonds to metals.
40. Due to symmetrical electronic configuration
there is no orbital contribution in Cr3+ ion.
However appreciable orbital contribution takes
place in Co2+ ion.
41. It is because in the beginning, when 5f
orbitals begin to be occupied, they will penetrate
less into the inner core of electrons. The 5f
electrons will therefore, be more effectively
shielded from the nuclear charge than 4f
electrons of the corresponding lanthanoids.
Therefore outer electrons are less firmly held and
they are available for bonding in the actinoids.
42. Due to lanthanoid contraction, they have
almost same size (Zr, 160 pm) and (Hf, 159 pm).
43. It is because after losing one more electron
Ce acquires stable 4f 0 electronic configuration.
44. KMnO4 acts as oxidising agent. It oxidises
oxalic acid to CO2 and itself changes to Mn2+ ion
which is colourless.
45. Dichromate Chromate
(Orange) (Yellow)
46. Oxidising behaviour of KMnO4 depends on
pH of the solution.
In acidic medium (pH < 7) MnO4 – + 8H+ + 5e–
→ Mn2+ (colourless) + 4H2O
In alkaline medium (pH>7) MnO4 – + e– →
MnO4 2– (Green)
In neutral medium (pH=7) MnO4 – + 2H2O +
3e– → MnO2 + 4OH – (Brown precipitate)
47. Due to lanthanoid contraction, the atomic
radii of the second and third row transition
elements is almost same. So they resemble each
other much more as compared to first row
elements.
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48.High ionisation enthalpy to transform Cu(s)
to Cu2+ (aq) is not balanced by its hydration
enthalpy. However, in case of Zn after removal
of electrons from 4s-orbital, stable 3d10
configuration is acquired.
49. As the oxidation state increases, size of the
ion of transition element decreases. As per
Fajan’s rule, as the size of metal ion decreases,
covalent character of the bond formed increases.
50. n + l rule : For 3d = n + l = 5 4s = n + l = 4
So electron will enter in 4s orbital. Ionisation
enthalpy is responsible for the ionisation of
atom. 4s electrons are loosely held by the
nucleus. So electrons are removed from 4s
orbital prior to 3d.
51. It is due to regular increase in ionisation
enthalpy
IV. Matching Type
52. (i) → (c) (ii) → (d) (iii) → (b) (iv) → (e) (v)
→ (a)
53. (i) → (b) (ii) → (a) (iii) → (d) (iv) → (e) (v)
→ (c)
54. (i) → (c) (ii) → (a) (iii) → (b)
55. (i) → (c) (ii) → (a) (iii) → (e) (iv) → (b)
56. (i) → (d) (ii) → (a) (iii) → (b) (iv) → (e) (v)
→ (f)
57. (i) → (b) (ii) → (d) (iii) → (a) (iv) → (e) (v)
→ (c)
58. (i) → (c) (ii) → (d) (iii) → (b) (iv) → (a)
V. Assertion and Reason Type
59. (i) 60. (ii) 61. (iii) 62. (i) 63. (ii)
VI. Long Answer Type
64. A = Cu ,B = Cu(NO3 )2 ,C = [Cu(NH3 )4 ] ,D
= CO2 ,E = CaCO3 ,
F = Cu2 [Fe(CN)6 ] ,G = Ca (HCO3 )2
65. A = FeCr2O4 ,B = Na2CrO4 ,C = Na2Cr2O7
.2H2O ,D = K2Cr2O7
66. A = MnO2 ,(B) K2MnO4 ,(C) KMnO4 ,(D)
KIO3
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 CHAPTER

9 COORDINATION COMPOUNDS

➢ Molecular / Addition Compound :

Molecular / Addition compounds are formed when stoichiometric amounts of two or more simple
compounds join together. Molecular / Addition compounds are of two types.

Double salts: Those which retain their identity in solutions are called double salts. For example
KCl + MgCl2 + 6H2O KCl.MgCl2. 6H2O
carnallite
K2SO4 + Al2(SO4)3 + 24 H2O K2SO4.Al2(SO4)3.24H2O
Potash alum
Complex compounds: Those which lose their identity in solution (complexes). For example
CuSO4 + 4 NH3 CuSO4.4 NH3 or [ Cu(NH3)4]SO4
Tetrammine copper (II) sulphate
Fe(CN) 2 + 4 KCN Fe (CN) 2. 4KCN or K4[Fe(CN)6]
Potassium ferryocyanide

DOUBLE SALTS COORDINATION COMPOUNDS

➢ Representation of Complex Ion : [MLx]n+

Where,
M = Central Metal atom /ion (usually of d-block)
L = Ligand
x = No. of ligands
n+ = charge on coordination complex
Outside region apart from coordination sphere is called ionization sphere.
JMD ੴ

1. Central metal atom/ion: Central ion acts as an acceptor (Lewis acid) and has to accommodate electron
pairs donated by the donor atom of the ligand, it must have empty orbitals. This explains why the transition
metals having empty d-orbitals form co-ordination compounds readily.

2. Ligands: Species which are directly linked with the central metal atom/ ion in a complex ion are called
ligands. The ligands are attached to the central metal atom /ion through co-ordinate or dative bond free
ligands have at least one lone pair.

Ligands can be of following types depending on the number of donor atoms pesent in them.
(i) Mono / Unidentate Ligands They have one donor atom, i.e., they can donate only one electron pair to
the central metal atom /ion eg., F–, Cl–, Br–, H2O, NH3, CN–,NO2–, OH–, CO etc.
(ii) Bidentate Ligands Ligands which have two donor atoms and have the ability to link with the central
metal atom /ion at two position are called bidentate ligands e.g.
ethylenediamine (en),oxalate (ox)
(iii) Hexadentate Ligands They have six donor atoms. The most important example is ethylenediamine
tetraacetate ion.(EDTA)
(iv) Ambidentate ligands : There are certain ligands which have two or more donor atoms but in forming
complexes, only one donor atom is attached to the metal / ion. Such ligands are called ambidentate ligands.
Some examples of such ligands are
NO2 or ONO–
nitrite – N nitrite –O
(v) Ligands having more than two donor atoms are called polydentate or multidentate ligands. Multidentate
ligands are known as a chelating ligands, it results in the formation of a stable cyclic ring thus, and the
complexes formed are called chelates. Chelating ligands are usually organic compounds.

3. Co-ordination sphere The central metal atom and the ligands directly attached to it are collectively
termed as the co-ordination sphere. Co-ordination sphere is written inside square brackets.

4. Co-ordination number (CN) The co-ordination number (CN) of a metal atom /ion in a complex is the
total number of e– pairs accetpted by central metal atom /ion from ligands through coordinate bond.

5.Oxidation state (O.S.) of central metal ion It is a number(numerical value) which represents the electric
charge on the central metal atom of a complex ion. For example the oxidation number of Fe, CO and Ni in
[Fe(CN)6]4–, [Co(NH3)6]3+ and Ni(CO)4 are +2, +3 and zero, respectively

➢ IUPAC NOMENCLATURE OF COMPLEXES:

The rules for the systematic naming of co-ordination compounds are as follows.
(i) The positive part is named first followed by the negative part, whether it is simple or complex.
(ii) In naming of a complex ion, the ligands are named first in alphabetical order, followed by naming of
central metal atom /ion.
(iii) When there are several monodentate ligands of the same kind, then we normally use the prefixes di,
tri,tetra, penta and hexa to show the number of ligands of that type. If ligand’s name already contain any of

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these prefix , then to avoid confusion in such cases, bis, tris and tetrakis are used instead of di, tri and tetra
and name of the ligand is placed in parenthesis. For example, bis(ethylene diamine) for two en-ligands.
(iv) Negative ligands have suffix-o, positive ligands have suffix -ium, where as neutral ligands have no
specific suffix. The names of negative ligands ending with -ide are changed to ‘o’.

Positive groups end with -ium. For example, NH2 – NH3+ (hydrazinium) NO+ (nitrosonium)
(v) Neutral ligands have No special ending and usually common ligands are provided to neutral ligands
except NH3 (ammine) H2O (aqua) CO (carbonyl), NO(Nitrosyl).
(vi) The oxidation state of the central metal ion is shown by Roman numeral in brackets immediately
following its name.
(vii) Complex positive ions and neutral molecules have no special ending but complex negative ions end
with -ate. suffix.
(ix) Ambidentate ligands may be attached through different atoms. Thus, M–NO2 is called N-nitrito and
M–ONO is called O-nitrito. Similarly M–SCN (thiocyanato) or M–NCS (Isothiocyanato). These may be

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named systematically, thiocyanato–S and thiocyanate –N respectively to indicate which atom is bonded to
the metal.
These rules are illustrated by the following examples.

➢ BONDING IN COMPLEXES

Werner’s Co-ordination Theory:

Alfred Werner put forward his concept of secondary valency for advancing a correct explanation for the
characteristics of the coordination compounds. The fundamental postulates of Werner’s theory are as
follows.
(i) Metal possess two types of valencies, namely, primary (principal or ionisable) valency and
secondary(auxillary or non-ioisable) valency.In modern terminology, the primary valency corresponds to
oxidation number and secondary valency to coordination number. According to werner primary valencies
are shown by dotted lines and secondary valencies by thick lines.
(ii) Primary valency is satisfied by negative ions, whereas secondary valency is satisfied either by negative
ions or by neutral molecules.
(iii) Primary valency has non-directional character, whereas secondary valency has directional character,
there fore a complex ion has its definite geometry.

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(iv) It is the directional nature of secondary valency due to which co-ordination compound exhibits the
phenomenon of isomerism.

Valence Bond Theory:

It was developed by Pauling. The salient features of the theory are summarized below:
(i) Under the influence of a strong field ligands like Cyanide or Carbonyl, the electrons of central metal ion
can be forced to pair up against the Hund’s rule of maximum multiplicity.
(ii) Under the influence of weak field ligands, electronic configuration of central metal atom / ion remains
same.
(iii) The central metal ion has a number of empty orbitals for accommodating electrons donated by the
ligands.The number of empty orbitals is equal to the co-ordination number of the metal ion for a particular
complex.
(iv) The atomic orbital (s, p or d) of the metal ion hybridize to form hybrid orbitals with definite directional
properties. These hybrid orbitals now accept e– pairs from ligands to form coordination bonds.
(v) The d-orbitals involved in the hybridization may be either inner (n – 1) d orbitals or outer n d-orbitals.
The complexes formed in these two ways are referred to as inner orbital complexes and outer orbial
complexes, respectively.

NOTE: If after hybridisation more than one electron are unpaired then it will be high spin complex
otherwise in all other cases it will be considered as low spin complex.

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Limitations of valence bond theory

(i) Correct magnetic moment of complex compounds cannot be theoretically measured by Valence bond
theory.
(ii) The theory does not offer any explanation about the spectra of complex (i.e., why most of the complexes
are coloured).
(iii) Theory does not offer any explanation for the existence of inner -orbital and outer -orbital complexes.
(iv) Assumptions of strong or weak ligands.

Crystal Field Theory (CFT) :

Crystal field theory is now much more widely accepted than the valence bond theory. It is assumed that the
attraction between the central metal and ligands in a complex is purely electrostatic (ionic). The transition
metal which forms the central atom cation in the complex is regarded as a positive ion of charge equal to
the oxidation state. It is surrounded by negative ligands or neutral molecules which have a lone pair of
electrons in the crystal field theory, the following assumptions are made.
(i) Ligands are treated as point charges.
(ii) There is no interaction between metal orbitals and ligands orbitals.
(iii) All the d orbitals on the metal have the same energy (that, is degenerate) in the free atom.

In order to understand clearly the crystal field interactions in transition metal complexes, it is necessary to
have knowledge of the geometrical or spatial disposition of d orbitals. The d-orbitals are fivefold
degenerate in a free gaseous metal ion. If a spherically symmetric field of negative ligand filed charge is
imposed on a central metal ion, the d-orbitals degeneracy will be affected.

Crystal Field Splitting in Octahedral Complex

• In the case of an octahedral coordination compound having six ligands surrounding the metal
atom/ion, we observe repulsion between the electrons in d orbitals and ligand electrons.
• This repulsion is experienced more in the case of dx2-y2 and dz2 orbitals as they point towards the axes
along the direction of the ligand.
• Hence, they have higher energy than average energy in the spherical crystal field.
• On the other hand, dxy, dyz, and dxz orbitals experience lower repulsions as they are directed between
the axes.
• Hence, these three orbitals have less energy than the average energy in the spherical crystal field.
Thus, the repulsions in octahedral coordination compound yield two energy levels:

t2g– set of three orbitals (dxy, dyz and dxz) with lower energy

eg – set of two orbitals (dx2-y2 and dz2) with higher energy

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This splitting of degenerate level in the presence of ligand is known as crystal field splitting. The
difference between the energy of t2g and eg level is denoted by “Δo” (subscript o stands for octahedral).
Some ligands tend to produce strong fields thereby causing large crystal field splitting whereas some
ligands tend to produce weak fields thereby causing small crystal field splitting.

Crystal Field Splitting in Tetrahedral Complex

The splitting of fivefold degenerate d orbitals of the metal ion into two sets will be opposite to that of
octahedral. The electrons in dx2-y2 and dz2 orbitals are less repelled by the ligands than the electrons
present in dxy, dyz, and dxz orbitals as the approach of the ligands are from between the axes. As a result,
the energy of dxy, dyz, and dxz orbital set are raised while that of the dx2-y2 and dz2 orbitals are lowered.

Thus, the repulsions in tetrahedral coordination compound yield two energy levels:

t2– set of three orbitals (dxy, dyz and dxz) with higher energy

e – set of two orbitals (dx2-y2 and dz2) with lower energy

The crystal field splitting in a tetrahedral complex is smaller in an octahedral its almost 4/9 of octahedral
energy gap and thus tetrahedral complexes are usually high spin as their electrons remained unpaired.

Crystal Field Stabilization Energy (CFSE)

The energy difference between the eg and t2g levels is given as or 10Dq. It states that each electron that
goes into the lower t2g level stabilizes the system by an amount of -4Dq and the electron that goes into
eg level destabilizes the system by +6Dq. That is the t2g is lowered by 4Dq and the eg level is raised by
+6Dq.
The decrease in energy caused by the splitting of the energy levels is called the “Ligand Field
Stabilization Energy (LFSE)”.

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Thus, the crystal field splitting depends on the field produced by the ligand and the charge on the metal
ion. An experimentally determined series based on the absorption of light by coordination compound with
different ligands known as spectrochemical series has been proposed. Spectrochemical series arranges
ligands in order of their field strength as:
I– < Br– < Cl– < SCN– < F– < OH– < C2O42- < H2O < NCS– < EDTA4- < NH3 < en < CN–< CO
Filling of d-orbitals takes place in the following manner; the first three electrons are arranged in t2g level
as per the Hund’s rule. The fourth electron can either enter into t2g level giving a configuration of t2g4eg0 or
can enter the eg orbital giving a configuration of t2g3eg1. This depends on two parameters magnitude of
crystal field splitting, Δo and pairing energy, P. The possibilities of two cases can better be explained as:

• Δo > P – Electron enters in the t2g level giving a configuration of t2g4eg0. Ligands producing this
configuration are known as strong field ligands and form low spin complexes.
• Δo < P – Electron enters in the eg level giving a configuration of t2g3eg1. Ligands producing this
configuration are known as weak field ligands and form high spin complexes.

Effective Atomic Number Rule

Effective Atomic Number Rule is proposed by Sidgwick. The total number of electrons passed by central
transition metal ion after the donation of electrons by the ligand an effective atomic number.
A complex is stable if the effective atomic number is equal to the atomic number of nearest inert gas.
Example: Calculate the effective atomic number of the following complexes:

• K4[Fe(CN)6]
• [Co(NH3)]Cl3

1. K4[Fe(CN)6]
Number of electrons in Fe2+ = 24
Number of electrons by Six CN = 2×6 = 12
Total number of electrons possessed by Fe2+ = 24 + 12
Therefore, the effective atomic number = 36.
2. [Co(NH3)]Cl3
Number of electrons in Co+3 = 24
Number of electrons by Six NH3 = 2×6 = 12
Total number of electrons possessed by Co+3 = 24 + 12
Therefore, the effective atomic number = 36.

METAL CARBONYLS
Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. The
general formula of metal carbonyls is Mx(CO)y.. A lone pair of electrons are available on both carbon
and oxygen atoms of a carbon monoxide ligand. As the carbon atoms donate electrons to the metal,
these complexes are named carbonyls.

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In a metal carbonyl, the metal-carbon bond possesses both the σ and π character. The bond between the
carbonyl molecule and the metal is further strengthened by the synergic effect produced by the metal-ligand
bond. The two types of bonding that exist in metal carbonyls are explained below:
Structure of Metal Carbonyls:

• Due to the donation of electrons by the carbonyl molecules to the vacant orbitals of the metal, a
metal-carbon σ bond is formed.
• Due to the donation of a pair of electrons from a filled d orbital metal into the vacant anti-bonding
π* orbital of carbonyl ligand, a metal-carbon π bond is formed.

Examples

APPLICATION OF COMPLEXES

The complexes are of immense importance on account of their applications in various fields. During
complex formation there are drastic changes in the properties of metal atom/ion these changes in properties
are made use of in the application of metal complexes.
(i) The detection and estimation of Ni2+ is based on the formation of a scarlet red complex with dimethyl
glyoxime.
EDTA is used as a complexing agent in volumeter analysis of metal ions like Ca2+, Mg2+ and Zn2+.
(ii) Metallurgical process: Silver and gold are extracted by the use of complex formation. Silver ore is
treated with sodium cyanide solution with continuous passing of air through the solution. Silver dissolves
as a cyanide complex and silver is precipitated by the addition of scrap zinc.
Nickel is extracted by converting it into a volatile complex, nickel carbonyl, by use of carbon monoxide
(Mond's process). The complex decomposes on heating again into pure nickel and carbon monoxide.
(iii) Photography In photography, the image on the negative is fixed by dissolving all the remaining silver
bromide with hypo solution in the form of a soluble complex.
(iv) Electroplating Metal complexes release metal slowly and give a uniform coating of the metal on the
desired object Cyano complexes of silver, gold copper and other metals are used for the electrodeposition
of these metals,
(v) Biological processes Metal complexes are of immense importance in biological processes.
Haemoglobin ,the red blood pigment, which acts as oxygen carrier to different parts of the body is a complex

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of iron(II). Vitamin B12 is a complex of cobalt metal. The green colouring matter of plants, called
chlorophyll, is a complex of magnesium. It acts as a catalyst in photosynthesis.

PRACTICE QUESTIONS

1. Using valence bond theory, predict the structure and the magnetic behavior of the below given complexes
and also their IUPAC names

a) [Fe(CN)6 ]4- h) [Fe(CO)5] p) [Fe(H2O)6 ]3+

b) [Fe(CN)6 ]3- i) [MnCl4]2- q) [Mn(CN)6 ]4-

c) [NiCl4]2- j) [CoF6 ]3- r) [FeF6]3-

d) [Ni(CN)4]2- k) [Co(en)3]3+ s) [MnCl6]3-

e) [Cr(NH3)6 ]3+ m) [Co(C2O4)3]3- t) [MnBr4]2-

f) [Co(NH3)6 ]3+ n) [Mn(CN)6 ]3-

g) [Ni(CO)4] o) [Ni(NH3)6 ]3+

2. A coordination compound has the formula CoCl3.4NH3. It does not liberate ammonia but gives
precipitate of AgCl with AgNO3 solution. Give the structural formula and IUPAC name of the complex.

3. Account for the following:

a) [Fe(CN)6]4- is diamagnetic while [Fe(CN)6]3- is paramagnetic.

b) [NiCl4]2- is tetrahedral while [Ni(CN)4]2- is square planar.
c) Hydrated copper sulphate is colored while anhydrous copper sulphate is colorless.
d) [Ti(H2O)6]3+ become colorless on heating.
e) [Ni(H2O)6]2+ is green while [Ni(CN)4]2- is colorless.
f) [Fe(CN)6]4- and [Fe(H2O)6]2+ show different colors in aqueous solution..
g) [Cr(NH3)6]3+ is paramagnetic while[Ni(CN)4]2- is diamagnetic.

4. A metal ion Mn+ having d4 configuration combine with three didentate ligand to form a
complex compound. Assuming ∆0>P

i) Draw the diagram showing d orbital splitting during this complex formation.
ii) Write the electronic configuration of the valence electron of the metal Mn+ ion in terms of t2g and
eg.
iii) What type of hybridisation will Mn+ ion have?
iv) Draw the structure of isomers exhibited by this complex.

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➢ NCERT EXEMPLAR 6. The stabilisation of coordination compounds due

to chelation is called the chelate effect. Which of
the following is the most stable complex
1. Which of the following complexes formed by species?
Cu2+ ions is most stable? (i) [Fe(CO)5]
(ii) [Fe(CN)6]3–
(iii) [Fe(C2O4)3]3–
(iv) [Fe(H2O)6]3+

7. Indicate the complex ion which shows

geometrical isomerism.
2. The colour of the coordination compounds
(i) [Cr(H2O)4Cl2]+
depends on the crystal field splitting. What will
(ii) [Pt(NH3)3Cl]
be the correct order of absorption of wavelength
(iii) [Co(NH3)6]3+
of light in the visible region, for the complexes,
(iv) [Co(CN)5(NC)]3-
[Co(NH3)6]3+ , [Co(CN)6]3-, [Co(H2O)3]3+
(i) [Co(CN)6]3- > [Co(NH3)6]3+ > [Co(H2O)6]3+
8. The CFSE for octahedral [CoCl6]4– is 18,000 cm-
(ii) [Co(NH3)6]3+ > [Co(H2O)6]3+ > [Co(CN)6]3- 1
. The CFSE for tetrahedral [CoCl4]2- will be
(iii) [Co(H2O)6]3+ > [Co(NH3)6]3+ > [Co(CN)6]3-
(i) 18,000 cm-1
(iv) [Co(CN)6]3- > [Co(NH3)6]3+ > [Co(H2O)6]3+
(ii) 16,000 cm-1
(iii) 8,000 cm-1
3. When 0.1 mol CoCl3(NH3)5 is treated with
(iv) 20,000 cm-1
excess of AgNO3,0.2 mol of AgCl are obtained.
The conductivity of solution will correspond to
9. Due to the presence of ambidentate ligands
(i) 1:3 electrolyte
coordination compounds show isomerism.
(ii) 1:2 electrolyte
Palladium complexes of the type
(iii) 1:1 electrolyte
[Pd(C6H5)2(SCN)2] and [Pd(C6H5)2(NCS)2] are
(iv) 3:1 electrolyte
(i) linkage isomers
(ii) coordination isomers
4. When 1 mol CrCl3⋅6H2O is treated with excess
(iii) ionisation isomers
of AgNO3, 3 mol of AgCl are obtained. The
(iv) geometrical isomers
formula of the complex is :
(i) [CrCl3(H2O)3]⋅3H2O
10. The compounds [Co(SO4)(NH3)5]Br and
(ii) [CrCl2(H2O)4]Cl⋅2H2O
[Co(SO4)(NH3)5]Cl represent
(iii) [CrCl(H2O)5]Cl2⋅H2O (i) linkage isomerism
(iv) [Cr(H2O)6]Cl3 (ii) ionisation isomerism
(iii) coordination isomerism
5. The correct IUPAC name of [Pt(NH3)2Cl2] is (iv) no isomerism
(i) Diamminedichloridoplatinum (II)
(ii) Diamminedichloridoplatinum (IV) 11. A chelating agent has two or more than two
(iii) Diamminedichloridoplatinum (0) donor atoms to bind to a single metal ion. Which
(iv) Dichloridodiammineplatinum (IV) of the following is not a chelating agent?
(i) thiosulphato
(ii) oxalato

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 JMD ੴ

(iii) glycinato 17. Which of the following options are correct for
(iv) ethane-1,2-diamine [Fe(CN) 6 ] complex?
(i) d2 sp3 hybridisation
12. Which of the following species is not expected to
(ii) sp3d2 hybridisation
be a ligand?
(iii) paramagnetic
(i) NO
(iv) diamagnetic
(ii) NH4+
(iii) NH2CH2CH2NH2
18. An aqueous pink solution of cobalt(II) chloride
(iv) CO
changes to deep blue on addition of excess of
HCl. This is because____________.
13. What kind of isomerism exists between
(i) [Co(H2O)6]2+ is transformed into [CoCl6]4-
[Cr(H2O)6]Cl3 (violet) and [Cr(H2O)5Cl]Cl2⋅H2O
(ii) [Co(H2O)6]2+ is transformed into [CoCl4]2-
(greyish-green)?
(iii) tetrahedral complexes have smaller crystal
(i) linkage isomerism
field splitting than octahedral complexes.
(ii) solvate isomerism
(iv) tetrahedral complexes have larger crystal
(iii) ionisation isomerism
field splitting than octahedral complex.
(iv) coordination isomerism

19. Which of the following complexes are

14. IUPAC name of [Pt(NH3)2Cl(NO2)] is :
homoleptic?
(i) Platinum diaminechloronitrite
(i) [Co(NH3)6]3+
(ii) Chloronitrito-N-ammineplatinum (II)
(ii) [Co(NH3)4Cl2]+
(iii) Diamminechloridonitrito-N-platinum (II)
(iii) [Ni(CN)4]2-
(iv) Diamminechloronitrito-N-platinate (II)
(iv) [Ni(NH3)4Cl2]
Multiple Choice Questions (Type-II)
20. Which of the following complexes are
Note : In the following questions two or more
heteroleptic?
options may be correct.
(i) [Cr(NH3)6]3+
15. Atomic number of Mn, Fe and Co are 25, 26 and
(ii) [Fe(NH3)4Cl2]+
27 respectively. Which of the following inner
(iii) [Mn(CN)6]4-
orbital octahedral complex ions are diamagnetic?
(iv) [Co(NH3)4Cl2]
(i) [Co(NH3)6]3+
(ii) [Mn(CN)6]3-
21. Identify the optically active compounds from the
(iii) [Fe(CN)6]4-
following :
(iv) [Fe(CN)6]3-
(i) [Co(en)3]3+
(ii) trans– [Co(en)2Cl2]+
16. Atomic number of Mn, Fe, Co and Ni are 25, 26
(iii) cis– [Co(en)2Cl2]+
27 and 28 respectively. Which of the following
(iv) [Cr (NH3)5Cl]
outer orbital octahedral complexes have same
number
22. Identify the correct statements for the behaviour
(i) [MnCl6]3-
of ethane-1, 2-diamine as a ligand.
(ii) [FeF6]3-
(i) It is a neutral ligand.
(iii) [CoF6]3-
(ii) It is a didentate ligand.
(iv) [Ni(NH3)6]2+
(iii) It is a chelating ligand.
(iv) It is a unidentate ligand.

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23. Which of the following complexes show linkage 34. CuSO4.5H2O is blue in colour while CuSO4 is
isomerism? colourless. Why?
(i) [Co(NH3)5(NO2)]2+ 35. Name the type of isomerism when ambidentate
(ii) [Co(H2O)5CO]3+ ligands are attached to central metal ion. Give
(iii) [Cr(NH3)5SCN]2+ two examples of ambidentate ligands.
(iv) [Fe(en)2Cl2]+
Matching Type Questions
Short Answer Type Questions Note : In the following questions match the
24. Arrange the following complexes in the items given in Columns I and II.
increasing order of conductivity of their solution: 36. Match the complex ions given in Column I with
[Co(NH3)3Cl3], [Co(NH3)4Cl2]Cl, the colours given in Column II and assign the
[Co(NH3)6]Cl3, [Cr(NH3)5Cl]Cl2 correct code :
25. A coordination compound CrCl3⋅4H2O
precipitates silver chloride when treated with
silver nitrate. The molar conductance of its
solution corresponds to a total of two ions. Write
structural formula of the compound and name it.
26. A complex of the type [M(AA)2X2]n+ is known
to be optically active. What does this indicate
about the structure of the complex? Give one
example of such complex.
37. Match the coordination compounds given in
27. Magnetic moment of [MnCl4]2– is 5.92 BM.
Column I with the central metal atoms given in
Explain giving reason.
Column II and assign the correct code :
28. On the basis of crystal field theory explain why
Co(III) forms paramagnetic octahedral complex
with weak field ligands whereas it forms
diamagnetic octahedral complex with strong
field ligands.
29. Why are low spin tetrahedral complexes not
formed?
30. Give the electronic configuration of the
following complexes on the basis of Crystal 38. Match the complex ions given in Column I with
Field Splitting theory. the hybridisation and number of unpaired
[CoF6]3- , [Fe(CN)6]4- and [Cu(NH3)6]2+. electrons given in Column II and assign the
31. Explain why [Fe(HO)6]3+ has magnetic moment correct code :
value of 5.92 BM whereas
[Fe(CN)6]3- has a value of only 1.74 BM.
32. Arrange following complex ions in increasing
order of crystal field splitting energy (ΔO) :
[Cr(Cl)6]3– , [Cr(CN)6]3–, [Cr(NH3)6]3+.
33. Why do compounds having similar geometry
have different magnetic moment?

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39. Match the complex species given in Column I
with the possible isomerism given in Column II
and assign the correct code :
40. Match the compounds given in Column I with
the oxidation state of cobalt present in it (given
in Column II) and assign the correct code.
Assertion and Reason Type Questions
Note : In the following questions a statement of
assertion followed by a statement of reason is
given. Choose the correct answer out of the
following choices.
(i) Assertion and reason both are true, reason is
correct explanation of assertion.
(ii) Assertion and reason both are true but reason
is not the correct explanation of assertion.
(iii) Assertion is true, reason is false.
(iv) Assertion is false, reason is true.
41. Assertion : Toxic metal ions are removed by the
chelating ligands.
Reason : Chelate complexes tend to be more
stable.
42. Assertion : [Cr(H2O)6]Cl2 and [Fe(H2O)6]Cl2 are
reducing in nature.
Reason : Unpaired electrons are present in their
d-orbitals.
43. Assertion : Linkage isomerism arises in
coordination compounds containing ambidentate
ligand.
Reason : Ambidentate ligand has two different
donor atoms.
44. Assertion : Complexes of MX6 and MX5 L type
(X and L are unidentate) do not show
geometrical isomerism.
Reason : Geometrical isomerism is not shown by
complexes of coordination number 6.
45. Assertion : ([Fe(CN)6]3- ion shows magnetic
moment corresponding to two unpaired
electrons.
Reason : Because it has d2sp3 type hybridisation.
Long Answer Type Questions
46. Using crystal field theory, draw energy level
diagram, write electronic configuration of the
central metal atom/ion and determine the
magnetic moment value in the following :
(i) [CoF6]3– , [Co(H2O)6]2+, [Co(CN)6]3–
(ii) [FeF6]3– , [Fe(H2O)6]2+ , [Fe(CN)6]4–
47. Using valence bond theory, explain the
following in relation to the complexes given
below:
[Mn(CN) 6 ]3– , [Co(NH3)6]3+ , [Cr(H2O)6]3+ ,
[FeCl6]4–
(i) Type of hybridisation.
(ii) Inner or outer orbital complex.
(iii) Magnetic behaviour.
(iv) Spin only magnetic moment value.
48. CoSO4 Cl.5NH3 exists in two isomeric forms ‘A’
and ‘B’. Isomer ‘A’ reacts with AgNO 3 to give
white precipitate, but does not react with BaCl2.
Isomer ‘B’ gives white precipitate with
BaCl2 but does not react with AgNO3 . Answer
the following questions.
(i) Identify ‘A’ and ‘B’ and write their structural
formulas.
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(ii) Name the type of isomerism involved.
(iii) Give the IUPAC name of ‘A’ and ‘B’.
49. What is the relationship between observed colour
of the complex and the wavelength of light
absorbed by the complex?
50. Why are different colours observed in octahedral
and tetrahedral complexes for the same metal
and same ligands?
ANSWERS
I. Multiple Choice Questions (Type-I)
1. (ii) 2. (iii) 3. (ii) 4. (iv) 5. (i) 6. (iii) 7. (i) 8.
(iii) 9. (i) 10. (iv) 11. (i) 12. (ii) 13. (ii) 14. (iii)
II. Multiple Choice Questions (Type-II)
15. (i), (iii) 16. (i), (iii) 17. (i), (iii) 18. (ii), (iii)
19. (i), (iii) 20. (ii), (iv) 21. (i), (iii) 22. (i), (ii),
(iii) 23. (i), (iii)
III. Short Answer Type
24. [Co(NH3)3Cl3 ] < [Cr(NH3)5Cl]Cl <
[Co(NH3)5Cl]Cl2 < [Co(NH3)6 ]Cl3
25. [Co(H2O)4Cl2 ]Cl
(tetraaquadichloridocobalt(III) chloride)
26. An optically active complex of the type
[M(AA)2X2 ] n+ indicates cisoctahedral structure,
e.g. cis-[Pt(en)2Cl2 ] 2+ or cis-[Cr(en)2Cl2 ] +
27. The magnetic moment of 5.92 BM
corresponds to the presence of five unpaired
electrons in the d-orbitals of Mn2+ ion. As a
result the hybridisation involved is sp3 rather
than dsp2 . Thus tetrahedral structure of [MnCl4]
2–
complex will show 5.92 BM magnetic moment
value.
28. With weak field ligands; ∆O < p, the
electronic configuration of Co (III) will be t2g4
eg2 and it has 4 unpaired electrons and is
paramagnetic. With strong field ligands, ∆0 > p,
the electronic configuration will be t2g 6 eg0 . It
has no unpaired electrons and is diamagnetic.
29. Because for tetrahedral complexes, the
crystal field stabilisation energy is lower than
pairing energy.
30. [CoF6 ] 3–, Co3+(d6 ) t2g 4 eg 2 , [Fe(CN)6 ]4– ,
Fe2+(d6 ) t2g 6 eg0 , [Cu(NH3)6 ]2+ , Cu2+ (d 9) t2g6
eg3 ,
31. [Fe(CN)6 ] 3– involves d 2sp3 hybridisation
with one unpaired electron and [Fe(H2O)6 ] 3+
involves sp3d2 hybridisation with five unpaired
electrons. This difference is due to the presence
of strong ligand CN – and weak ligand H2O in
these complexes.
32. Crystal field splitting energy increases in the
order [Cr(Cl)6 ] 3–< [Cr(NH3)6 ] 3+ < [Cr(CN)6 ]3–
33. It is due to the presence of weak and strong
ligands in complexes, if CFSE is high, the
complex will show low value of magnetic
moment and vice versa, e.g. [CoF6 ]3– and
[Co(NH3)6 ]3+ , the former is paramagnetic and
the latter is diamagnetic.
34. In CuSO4 .5H2O, water acts as ligand as a
result it causes crystal field splitting. Hence d—d
transition is possible in CuSO4 .5H2O and shows
colour. In the anhydrous CuSO4 due to the
absence of water (ligand), crystal field splitting
is not possible and hence no colour.
35. Linkage isomerism
IV. Matching Type
36. (ii) 37. (i) 38. (ii) 39. (iv) 40. (i)
V. Assertion and Reason Type
41. (i) 42. (ii) 43. (i) 44. (ii) 45. (iv)
VI. Long Answer Type
47. [Mn(CN)6]3–
Mn3+ = 3d4 (i) d2sp3 (ii) Inner orbital complex
(iii) Paramagnetic (iv) 2(2 2) + = 8 = 2.87 BM
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JMD ੴ

[Co(NH3)6]3+

Co3+ = 3d6 (i) d2 sp3 (ii) Inner orbital complex

(iii) Diamagnetic (iv) Zero [Cr(H2O)6] 3+

Cr3+ = 3d3 (i) d2sp3 (ii) Inner orbital complex (iii)

Paramagnetic (iv) 3.87 BM

[Fe(Cl)6]4–

Fe2+ = 3d6 (i) sp3d2 (ii) Outer orbital complex

(iii) Paramagnetic (iv) 4.9 BM

48. (i) A - [Co(NH3)5SO4]Cl B -

[Co(NH3)5Cl]SO4 (ii) Ionisation isomerism (iii)
(A), Pentaamminesulphatocobalt (III) chloride
(B), Pentaamminechlorocobalt (III) sulphate.

49. When white light falls on the complex, some

part of it is absorbed. Higher the crystal field
splitting, lower will be the wavelength absorbed
by the complex. The observed colour of complex
is the colour generated from the wavelength left
over.

50. ∆t = ∆0 4/ 9 . So higher wavelength is

absorbed in octahedral complex than tetrahedral
complex for same metal and ligands.

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CHAPTER

10 HALOALKANE AND HALOARENE

Classification of Haloalkanes and Haloarenes

They can be classified on the basis of:

Number of Halogen atoms

Compounds with sp3 C—X Bond
Compounds having the sp2 C-X Bond

1) Number of Halogen Atoms:

On the basis of the number of halogen, they can be divided into mono, di or poly haloalkanes and
haloarenes.

2) Compounds with sp3 C—X Bond:

These compounds can be further divided into three types. They are:

i) Alkyl Halides/ Haloalkanes (R — X)

In this class, the halogen atom is attached to an alkyl group. The general homologous formula followed by
this class is CnH2n+1X. They are further classified into mainly three types on the basis of the carbon
atom to which the carbon-bearing halogen (X) atom is bonded- primary, secondary, and tertiary. This
classification is based on the nature of the carbon atom to which the halogen is attached.

ii) Allylic Halides

This classification of compounds is formed by bonding of halogen group having sp3 hybridized carbon
atom present next to a carbon-carbon double bond structure (C=C). The carbon-carbon double bond
structure is also known as allylic carbon. Thus, the name allylic halides.

(iii) Benzylic Halides

This type of compounds is formed when a halogen atom is attached to an SP3 hybridized carbon atom. The
SP3 hybridized carbon atom should be present next to an aromatic ring in order to form benzyl halides.

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3) Compounds Having the sp2 C-X Bond

This class of compounds includes vinyl halides and aryl halides.
i) Vinyl Halides
These compounds are formed when a halogen atom is attached to an SP2 hybridized carbon atom present
next to a carbon-carbon double bond (C=C).

ii) Aryl Halides

This class of compounds is formed when the halogen group is bonded to an sp2 hybridized atom of carbon
in an aromatic ring.

Nature of C-X Bond

The C-X bond is highly polar in nature because halogen atoms are electronegative and the
carbon atom is electropositive.
Therefore, the carbon-halogen bond of an alkyl halide is polarized. This is represented as:
Abnormal order of the dipole moment in the case where CH3CI > CH3F Even though fluorine is more
electronegative than Chlorine as the C-F bond (139 pm) is shorter than the C-CI bond C — CI (178 pm).
Thus, the dipole moment will be lower in the case of CH3F in comparison to CH3Cl.

METHODS OF PREPARATION (HALOALKANES)

1). FROM ALKANES: - (Halogenation, Substitution Reaction)

Both chlorination and Bromination can be achieved either upon by heating or in the presence of sunlight
(Photochemical Reactions). Normally, Reaction can’t be controlled at the monosubstitution level and thus
produces a mixture of different substituted products are difficult to separate. Thus, Halogenation is not
much preferred.
hv
CH₄ + Cl₂ CH₃Cl + CH₂Cl₂ +CHCl₃ + CCl₄ +HCl

2).FROM ALKENES :- (Addition Reaction)

• Symmetrical alkenes

CH₂ = CH₂ + H-Cl CH₃CH₂Cl

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• Unsymmetrical alkenes
R-CH(Cl)-CH₃ (2⁰) Markonikov’s rule

R- CH = CH₂ + H-Cl

R-CH₂CH₂Cl (1⁰) peroxide (anti markonikov’s)

• Addition of Bromine in CCl4 to an alkene resulting discharge of Reddish Brown colour and thus, useful
for the detection of Double bonds
CCl₄
CH₂ == CH₂ + Br₂ Br-CH₂ CH₂ Br

3). FROM ALCOHOLS :- (Substitution Reaction)

A) BY THE ACTION OF HALOGEN ACIDS

R OH +H- X R X + H₂O

For the above reaction,

• The ease of alcohols to give this reaction is 3⁰>2⁰>1 ⁰ (because greater No. of alkyl groups i.e EDG
conducts more + I effect which by donating electrons makes a 3o carbon efficient and stable such that it
can loose OH group easily)
• The ease of halo acids to give this reaction is H-I > H - B r > H - Cl (due to less bond dissociation
energy)
• Chloroalkanes can be prepared by reacting alcohol with HCl + Anyd.ZnCl2 (= called Lucas Reagent or
lindlar’s reagent). 1 ⁰, 2⁰ and 3⁰ alcolols reacts with lindlar’s reagent differently so, this reaction is used
to distinguish among alcohols.

B BY PHOSPHOROUS HALIDES:-

3R OH + PCl₃ 3R Cl +H₃PO₃

R OH + PCl₅ R Cl +POCl₃ +HCl

Reactions can be noted with PBr₃ and PI₃ but not with pentaderivatives of fluro and iodo as they does not
exists.

C. DARZAN’S METHOD: -

R OH + SOCl₂ R Cl + SO₂ + HCl

Mixing thionyl chloride and alcohol to produce Haloalkanes is a preferred way as the byproducts (SO₂ and
HCl) are gaseous in nature which can be easily escaped leaving haloalkane.
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4). HALOGEN EXCHANGE REACTION:

• So for fluorides use SWARTS REACTION

R X + AgF R F + AgX
(X= Cl, Br)

• For Iodides use FINKELSTIEN REACTION

R X + NaI R I + NaX
(X = Cl, Br)

Acetone is used to precipitate NaBr and NaCl so formed, as a result reaction shifted towards forward to
yield more product according to Le-Chatelier’s process.

PREPARATIONS OF HALOARENES:

1) FROM ARENES (Benzene) (Substitutions Reaction) (Halogenations)

Cl
+ Cl₂ (Anhydrous AlCl₃/feCl₃/fe) + HCl

2). FROM DIAZONIUM CHLORIDE:

• Benzene diazonium chloride needed is prepared from Aniline by treating it with HCl and an ice solution
on NaNO₂. This reaction is called as Diazotization Reaction
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PHYSICAL PROPERTIES (HALOALKANES AND HALOARENES)

The lower haloalkanes are gaseous at room temperature and from there upto 18 carbon atoms are liquid,
higher than that are solids at room temperature

Alkyl halides are colorless, however bromides and iodides develops color when exposed to air.

M.P/B.P: due to greater polarity and higher molecular masses of halo alkanes, as compared to the parent
hydrocarbons, the intermolecular forces of attraction (dipole-dipole and van der Waal) are stronger, so
boiling points of haloalkanes is higher than those of hydrocarbons.

M.P/B.P is directly proportional to molecular masses (greater molecular masses means more intermolecular
attractions)

M.P and B.P is inversely proportional to branching (branching causes decrease in density, which means
lesser compatibility and more intermolecular spaces which helps in combustion)

In dihalobenzenes, thus Para has more b.p/m.p than ortho and Meta because of symmetry and it fits in
crystal lattice better & compact.

SOLUBILITY: Haloalkanes are very slightly in water, as the newer bonds that formed b/w haloalkanes
and water molecules are not as strong as original hydrogen bonds. So, inspite of having polarity, haloalkanes
are immiscible in water because of inability to form hydrogen- bonds with water.

CHEMICAL REACTIONS OF HALOALKANES

NUCLEOPHILIC REACTION
ELIMINATION
SUBSTITUTION WITH ACTIVE
REACTION
REACTION METALS

A).NUCLEOPHILIC SUBSTITUTION REACTION

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• The above anomaly that with KCN, alky halides (haloalkenes) yields cyanide products and yields
isocyanides products with AgCN can be explained as :-
• KCN is predominantly ionic in nature and provides cyanide ions, although CN- is an ambident
nucleophile can attach from either of sides but in KCN , attaches from carbon as C-C bond is stable than
C-N bond. However AgCN is purely covalent in nature so, cyanide is free and due to more
electronegativity of N it attaches and forms Isocyanides products.
• Such reactions in which a stronger nucleophile displaces a weaker nucleophile are called Nucleophilic
Substitution (SN) reactions and the halide ion which departs with its bonding pair of electrons is called
the leaving group. The better the leaving group, the more facile is the nucleophile substitution
reaction. It follows the order
I– > Br > Cl– > F–
∴ The order of reactivity of haloalkanes follows the sequence Iodoalkanes > Bromoalkanes >
chloroalkanes > fluoroalkanes.

➢ Types of Nucleophilic Substitution reactions:

1. SN2 [Substitution, nucleophilic, bimolecular]

2. SN1 [Substitution, nucleophilic, unimolecular]

1. Substitution nucleophilic bimolecular (SN2):

The reaction between CH3Cl and hydroxide ion to yield methanol and chloride ion follows second-order
kinetics, i.e., the rate depends upon the concentration of both reactants.

Rate of reaction ∝ [Base] [R-X]

Since the rate of the reaction depends upon the concentration of both the reactants, it is a bimolecular
nucleophilic displacement reaction.
There occurs a complete stereochemical inversion of the configuration.
The order of reactivity of the alkyl halides is Primary halide > Secondary halide > Tertiary halide.
Governing step is unsatability of carbocation and no steric hindrance it means those which forms unstable
carbocation and having no steric hindrance undergoes one step SN2 faster.
In the SN2 reaction, the attack of the nucleophile (OH– above) occurs from the backside, and the halide ion
leaves from the front side. This inversion of configuration is called Walden Inversion. As far as the ease
of departure of halide ion is concerned, the order of reactivity is RI > RBr > RCl > RF.
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2. Substitution nucleophilic unimolecular (SN1)

SN1 reactions are generally carried out in polar protic solvents (like water, alcohol, acetic acid, etc). The
reaction between tert-butyl bromide and hydroxide ion yields tert-butyl alcohols and follows first-order
kinetics.
This reaction is independent of the concentration of the base. The rate law suggests the reaction proceeds in
two steps.

This step is slow and hence is the rate-detaining step.

This step, being fast, does not affect the rate of reaction. If the alkyl halide is optically active, then the
product is a racemic mixture.

Governing step is the stability of carbocation and thus, allylic and benzylic halides show high reactivity
towards SN1 reaction. The carbocation gets stabilized through resonance as shown bel

For a given alkyl group, the reactivity of the halide, R-X, follows the same order in both mechanisms.
R-I > R-Br > R-Cl > > R-F.
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Stereochemical aspects of nucleophilic substitution reactions: An SN2 reaction proceeds with complete
stereochemical inversion of configuration while an SN1 reaction proceeds with racemization.

➢ Optical Activity: Certain compounds exhibit the property of rotating the plane polarised light when it
passed through their solutions. Such compounds are called Optically Active compounds arid this
phenomenon is called Optical Activity.

If the compound rotates the plane-polarised light to the right, i.e., in a clockwise direction, it is called
dextro-rotatory or the d-form and is indicated by placing a positive (+) sign before the degree of rotation.
If the light is rotated towards the left (anticlockwise), the compound is said to be laevorotatory or the /-
form and a negative sign (-) is placed before the degree of rotation. Such (+) and (-) isomers of a
compound are called Optical Isomers and this phenomenon is termed Optical Isomerism.

All the physical properties of compounds showing optical activity are the same like refractive index
solubility, density, m.pts, b.pts, etc. Even the extent of rotation is the same. They differ from each other
only in the direction of rotation.
If all the substituents attached to the C atom are different, such a carbon atom is called asymmetric carbon
or stereocenter.

Butan-2-ol has 4 different groups attached to the tetrahedral carbon atom and is Chiral. The mirror image
of Butan-2-ol non-superimposable onbutan-2-ol

Other chiral molecules are Bromochloroiodimethane (BrCl CHI), 2-chlorobutanol, 2, 3-

dihydroxypropanal (OHC- CHOH-CH2OH), lactic acid (CH3CH(OH)COOH). The stereoisomers related
to each other as non-superimposable are also called Enantiomers and the concept Enantiomerism.

A mixture containing two enantiomers in equal proportions will have zero optical rotation, as the rotation
due to one isomer will be canceled by the rotation due to the other isomer. Such a mixture is called Racemic
Mixture or Racemic Modification. It is represented by prefixing dl or (±) before the name, e.g., (±) butan-
2-ol. The process of conversion of enantiomer into a racemic mixture is known as Racemization.
Inversion, retention, and racemization: These are three possibilities for a reaction to occur at an
asymmetric carbon atom. Consider the replacement of a group X and Y in the following reaction:
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If (A) is the only compound obtained, the process is called retention of configuration.
If (B) is the only compound obtained, the process is called inversion of configuration.
If a 50: 50 mixture of (A) and (B) is obtained, the process is called racemization and the product is
optically inactive.

ROLE OF SOLVENTS

Solvents are classified into polar and non-polar based on their capability to form charge separation. Polar
solvents are those with high dielectric constant, greater than 15 and non-polar solvents are those with a low
dielectric constant, less than 5. Higher the dielectric constant of the solvent, the higher will be the stability
of the carbocation and faster will be the rate of SN1 reaction

PROTIC

APROTIC
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B) ELIMINATION REACTION.

In an elimination reaction, two atoms or groups (YZ) are removed from the substrate
with the formation of a pi bond.

depending on the reagents and conditions involved, elimination may be a first-order (El) or
second-order (E2).

Characteristics of El reaction
1.It is a unimolecular, two-step process
2.It is a first-order reaction
3.Reaction intermediate is carbocation, so rearrangement is possible
4.In the second step, a base abstracts a proton from the carbon atom adjacent to the
carbocation and forms alkene.
5. Rate = k[Substrate]
Bimolecular reaction, second-order kinetic:

1. Leaving group leads when the base is taking proton from adjacent carbon.
2. It is a single step reaction
3. It shows elemental as well as kinetic isotopic effect
4. Normally Sayetzeff product is major.
5. Transition state mechanism therefore rearrangement is not possible.
6. The orientation of the proton & leaving group should be antiperiplanar for E2.
7. E2-elimination is favour by:

Strong base (RO-, AIC. KOH) High conc. of base.

Polar aprotic solvent. High temperature

• Reactivity towards E2: R - I > R - Br > R- Cl > R— F

• With alcoholic KOH, a β-hydrogen (β carbo’s hydrogen which is attached with α carbon which is turn
attached directly with the functional group.) Elimination Reaction takes place.

CH₃CH₂Cl + alc.KOH CH₂ CH₂ + KCl + H₂O

• In aqueous KOH, both KOH + water (H₂O) produces OH⁻(Hydroxide) Nucleophile which is turn brings
substitution reaction, while KOH in alcohol produces (K⁺ +OH⁻ and RO⁻ + H⁺) Alkoxide Nucleophile
which is a stronger Nucleophile and performs elimination by abstracting proton (H+) from Alkyl Halide

In case of possibility of forming two different positions of double bond then a more substituted alkene
is preferred, according to Sayetzeff’s Rule. It can be explained as a more substituted alkene (which has
the greater number of alkyl groups attached to the doubly bonded carbon atoms) can be more stabilized
through Hyper conjugation.
JMD ੴ

• An alkyl halide with β-hydrogen atoms when reacted with a base or a nucleophile has two competing
routes: substitution (SN1 and SN2) and elimination. The route to be taken up depends upon the nature of
alkyl halide, strength and size of base/nucleophile, and reaction conditions.

Thus, a bulky nucleophile abstracts a proton rather than approaches a tetravalent C atom (steric hindrance)
to undergo elimination over substitution. Similarly, a primary alkyl halide will prefer an SN2 reaction over
elimination as there is no steric hindrance.

(C) REACTION WITH ACTIVE METALS

1). WITH SODIUM (step up reaction called WURTZ REACTION)

R – X + 2Na + X – R R – R + NaX

Dry either is added as it’s a good Aprotic (No Hydrogen) which acts as a good solvent for all the compounds
present in the test tube

2). WITH MAGNESIUM (GRIGNARD’S REAGENT)

Anhydrous condition

R X + Mg R Mg X

As the compound Grignard reagent is highly reactive in nature and can react with any source of water even
from moisture, abstracts proton (H) and forms a stable product alkane
JMD ੴ
• CHEMICAL REACTIONS OF HALOARENES

REACTION OF HALOARENES (NUCLEOPHILIC SUBSTITUTION)

Aryl Halides are extremely less reactive towards Nucleophilic substitution reaction due to:-
(1) Partial double bond character acquired in C-X bond due to resonance
(2) In Haloalkane, Carbon atom is sp³ hybridized while in Haloarenes is sp² hybridized, so its has greater
s-character and electro negativity which holds c-x bond firmly, thus they have shorter bond length than
Haloalkane which is much stronger

H X Sp² hybridsed
Attached with 3
C sp³hybridised
other atoms due
R (attached with 4
to double bond
H X other atoms)

• Replacement by hydroxy group (formation of phenol)

When aryl halides are heated at 623 K and under pressure (300 atm), with aqueous solution of sodium
hydroxide, the halogen atom is replaced by hydroxyl group forming phenol. Firstly sodium phenoxide
is formed, which on acidification gives phenol.

This reaction forms the basis for the manufacture of phenol by Dow's process.
• Effect of substituents in haloarenes (aryl halides) on the reactivity
The reactivity of haloarenes is markedly affected by the presence of certain groups at certain positions
of the ring. The presence of electron withdrawing groups such as -NO2, -CN, -COOH, etc. at 'o' and 'p'
positions to the halogen atom, greatly activates the halogen towards nucleophilic substitution
reactions.

122
JMD ੴ

• The presence of a nitro group at ortho- and para- position withdraws the electron density from the
benzene ring and thus facilitates the attack of the nucleophile on haloarene.

• The carbanion thus formed is stabilized through resonance. The negative charge appeared at ortho-
and para- positions with respect to the halogen substituent is stabilized by -NO2 group while in the
case of meta-nitrobenzene, none of the resonating structures bear the negative charge on carbon
atom bearing the -NO2 group.

• Therefore, the presence of a nitro group of meta-position does not stabilize the negative charge and
no effect on reactivity is observed by the presence of the -NO2 group of meta-position.

➢ REACTION OF HALOARENES (ELECTROPHILIC SUBSTITUTION)

• Halogen on benzene ring acts as ortho para directive group, due to resonance, the electron density
at O- and P-positions increase than m-position, which makes it ortho and para directive.
• Further, halogen atom because of its –I effect withdraws e⁻ from benzene ring, and the ring gets
deactivated as compared to benzene and thus electrophilic substitution reactions in haloarenes occur
slowly than benzene and requires conditions for feasibility.
• Reactions will generate ortho and para product upon halogenation, nitration, sulphonation,and
friedal craft alkylation and acylation.
JMD ੴ

➢ NOTES:

• Chlorine Containing antibiotics, chloramphenicol (chloromycetin) produced by soil microorganism

is very effective in the treatment of typhoid fever.
• Our body produces an iodine containing hormone called thyroxine, the deficiency of which causes
the disease goitre.
• chloroquine is used for the treatment of malaria and halothane (CF3 - CHCIBr) is an anaesthetic
agent used during surgery.
• Chloroform can be used as an anaesthetic after being mixed with ether but due to harmful effects it
is not used these days for this purpose. It causes liver damage when inhaled in excess (so is CCl4).
Halothane (CF3CHCIBr) is less toxic than CHCl3 but a fluorine containing anaesthetic agent widely
used these days is isoflurane (F3C-CHCI-O- CHF2).
• When exposed to sunlight and air, chloroform slowly decomposes into carbonyl chloride
(phosgene) and hydrogen chloride.
• Phosgene is extremely poisonous gas. To use chloroform as an anaesthetic agent, it is necessary
toprevent this reaction. The two precautions, given ahead, are taken when chloroform is stored.

(a) It is stored in dark blue- or brown-coloured bottles which are filled upto the brim.

(b) 1% ethyl alcohol is added. This retards the oxidation and converts the phosgene formed into
harmless ethyl carbonate.

• Pure chloroform does not give white precipitate with aq. silver nitrate. It is because the C-Cl bond
in CHCl3 is covalent and does not ionize
• Iodoform is extensively used as an antiseptic for dressing of wounds; but the antiseptic action is
due to the liberation of free iodine and not due to iodoform itself.
• Carbon tetrachloride is used as a fire extinguisher under the name pyrene.
• DDT is used as an effective insecticide for mosquitoes, flies and crop pests. It was also an
important antimalarial, since it destroys anopheles mosquitoes which spread malaria.
• Benzene hexachloride (BHC) is used as a powerful insecticide under the name of gammexane or
666 or lindane. It is also used extensively as a pesticide in agriculture for killing termite (white
ants) from soil.
• Silver nitrate test it is used to distinguish aliphatic halides and aromatic halides as aliphatic
halides gives white precipitate of silver chloride.
This test is also so use to distinguish between aliphatic halide and vinyl halides as vinyl halides
do not undergo nucleophilic substitution reaction easily so, no white precipitate will be
observed in vinyl halides.

➢ SOME IMPORTANT LINES FROM NCERT

• In common name system, gem-dihalides are named as alkylidene halides and vic-dihalides are
named as alkylene dihalides. In IUPAC system, they are named as dihaloalkanes.

• Thionyl chloride (darzen’s process) is preferred because the other two products are escapable gases.
Hence the reaction gives pure alkyl halide
JMD ੴ

• Free radical chlorination or bromination of alkanes gives a complex mixture of isomeric mono- and
polyhaloalkanes, which is difficult to separate as pure compounds. Consequently, the yield of any
one compound is low.
• Reactions with iodine are reversible in nature and require the presence of an oxidising agent (HNO3,
HIO4) to oxidise the HI formed during iodination. Fluoro compounds are not prepared by direct
raections due to high reactivity of fluorine.
• In the laboratory, addition of bromine in CCl4 to an alkene resulting in discharge of reddish brown
colour of bromine constitutes an important method for the detection of double bond in a molecule.
The addition results in the synthesis of vic-dibromides, which are colourless
• Due to greater polarity as well as higher molecular mass as compared to the parent hydrocarbon, the
intermolecular forces of attraction (dipole-dipole and van der Waals) are stronger in the halogen
derivatives. That is why the boiling points of chlorides, bromides and iodides are considerably higher
than those of the hydrocarbons of comparable molecular mass.
• Boiling points of isomeric dihalobenzenes are very nearly the same. However, the para-isomers are
high melting as compared to their ortho and meta-isomers. It is due to symmetry of para-isomers
that fits in crystal lattice better as compared to ortho- and meta-isomers.
• Less energy is released when new attractions are set up between the haloalkane and the water
molecules as these are not as strong as the original hydrogen bonds in water. As a result, the
solubility of haloalkanes in water is low or they are immiscible though they are polar.
• Groups like cyanides and nitrites possess two nucleophilic centres and are called ambident
nucleophiles.
• Allylic and benzylic halides show high reactivity towards the SN1 reaction. The carbocation thus
formed gets stabilised through resonance.
• If all the substituents attached to that carbon are different, such a carbon is called asymmetric
carbon (chiral carbon) or stereocentre. The resulting molecule would lack symmetry and is
referred to as asymmetric molecule. The asymmetry of the molecule is responsible for the optical
activity in such organic compounds.
• The stereoisomers related to each other as non-superimposable mirror images are called
enantiomers while those which are non-superimposable and non-mirror images of each other
are called as diastreomers.
• Enantiomers possess identical physical properties namely, melting point, boiling point, solubility,
refractive index, etc. They only differ with respect to the rotation of plane polarised light. If one of
the enantiomer is dextro rotatory, the other will be laevo rotatory.
• Sayetzeff’s rule : In dehydrohalogenation reactions, the preferred product is that alkene which has
the greater number of alkyl groups attached to the doubly bonded carbon atoms.
• A bulkier nucleophile will prefer to act as a base and abstracts a proton rather than approach a
tetravalent carbon atom (steric reasons) and vice versa. Similarly, a primary alkyl halide will prefer
a SN2 reaction.
A secondary halide- SN2 or elimination depending upon the strength of base/nucleophile.
A tertiary halide- SN1 or elimination depending upon the stability of carbocation or the more
substituted alkene.
• Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons.
Even water, alcohols, amines are sufficiently acidic to convert them to corresponding hydrocarbons.
It is therefore necessary to avoid even traces of moisture from a Grignard reagent. On the other hand,
this could be considered as one of the methods for converting halides to hydrocarbons.
• The chlorofluorocarbon compounds of methane and ethane are collectively known as freons. They
are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable gases. Freon 12
(CCl2F2) is one of the most common freons in industrial use. It is manufactured from
JMD ੴ

tetrachloromethane by Swarts reaction. These are usually produced for aerosol propellants,
refrigeration and air conditioning purposes. In stratosphere, freon is able to initiate radical chain
reactions that can upset the natural ozone balance.
• Many species of insects developed resistance to DDT, and it was also discovered to have a high
toxicity towards fish. The chemical stability of DDT and its fat solubility compounded the problem.
DDT is not metabolised very rapidly by animals; instead, it is deposited and stored in the fatty
tissues. If ingestion continues at a steady rate, DDT builds up within the animal over time. The use
of DDT was banned in the United States in 1973.
JMD ੴ

PRACTICE QUESTIONS

Account for the following:

a) Haloalkanes have higher boiling point than the corresponding parent alkane.
b) Boiling point of halo alkanes RI>RBr>RCl> RF
c) Boiling point of 1-Bromo butane >2-Bromo butane> 1-Bromo- 2-methyl propane> 2-Bromo- 2-
methyl propane.
d) Melting point of p-Dichlo benzene is higher than its ortho and meta isomer.
e) Halo alkanes are polar in nature but sparingly soluble in water.
f) Iodo alkane can not be prepared by the reaction of alcohol with KI and sulphuric acid. Phosphoric
acid is used in place of sulphuric acid.
g) Order of reactivity of alcohol with HX is tert alcohol> sec alcohol > primary alcohol..
h) Halo arenes cannot be prepared by treating phenol with HX or NaX in the presence of sulphuric acid.
i) Iodination of benzene is carried out in the presence of HIO3 or HNO3.
j) Propane on chlorination gives 2-chloro propane as a major product and not 1-chloro propane.
k) Kharasch effect is possible only with HBr and not with HCl and HI.
l) Alcohol reacts with thionyl chloride to give pure halo alkane.
m) Finkelstein reaction of halo alkane is carried out in the presence of dry acetone.
n) Order of reactivity of halo alkanes as per substitution bimolecular nucleophilic is primary halide >
secondary halide>tertiary halide.
o) Order of reaction as per substitution unimolecular is tertiary halide>secondary halide >primary
halide.
p) Benzylic halides and allylic halides are more reactive towards nucleophile than halo alkanes.
q) Chloro ethene is less reactive towards nucleophile than chloro ethane.
r) Halo arenes are less reactive towards nucleophile than halo alkanes.
s) SN1 mechanism is ruled out in the reaction of halo arenes with nucleophile.
t) Electron with drawing groups like NO2 at ortho and para position with respect to halogen facilitates
nucleophillic substitution reaction.
u) Electron with drawing groups like NO2 at meta position with respect to halogen has no effect on
nucleophillic substitution reaction.
v) Halo arenes are less reactive towards electrophile than benzene.
w) Although chlorine atom has electron with drawing effect electrophillic substitution occur at ortho
and para position.
x) Order of reactivity of alkyl halide RI>RBr>RCl>RF
y) Halo alkanes react with KCN to give alkyl cyanide as a major product while it gives alkyl isocyanide
as a major product with AgCN.
z) Halo alkanes give nitrito alkane with KNO2 while nitro alkane with AgNO2.
aa) CH3I undergoes SN2 reaction faster than CH3Cl.
bb) Grignard reagents are prepared under anhydrous condition.
cc) Cyclohexyl chloride has greater dipole moment than Chlorobenzene.
 JMD ੴ
➢ EXEMPLAR QUESTIONS 5. Which of the following is halogen exchange
reaction?
1. The order of reactivity of following alcohols
with halogen acids is ___________.

2. Which of the following alcohols will yield the

corresponding alkyl chloride on reaction with
concentrated HCl at room temperature?
6. Which reagent will you use for the following
reaction ?

(i) Cl2/UV light

(ii) NaCl + H2SO4
(iii) Cl2 gas in dark
(iv) Cl2 gas in the presence of iron in dark
7. Arrange the following compounds in the
increasing order of their densities.

3. Identify the compound Y in the following

reaction.

8. Arrange the following compounds in

increasing order of their boiling points

9. In which of the following molecules carbon

atom marked with asterisk (*) is asymmetric?

4. Toluene reacts with a halogen in the presence

of iron (III) chloride giving ortho and para halo
compounds. The reaction is
(i) Electrophilic elimination reaction
(ii) Electrophilic substitution reaction (i) (a), (b), (c), (d)
(iii) Free radical addition reaction (ii) (a), (b), (c)
(iv) Nucleophilic substitution reaction (iii) (b), (c), (d)
(iv) (a), (c), (d)
10. Which of the following structures is
enantiomeric with the molecule (A) given
below :

125
 JMD ੴ

15. What is ‘A’ in the following reaction?

11. Which of the following is an example of vic-

dihalide?
(i) Dichloromethane 16. A primary alkyl halide would prefer to undergo
_____________.
(ii) 1,2-dichloroethane
(i) SN1 reaction
(iii) Ethylidene chloride
(ii) SN2 reaction
(iv) Allyl chloride (iii) α–Elimination
12. The position of –Br in the compound in (iv) Racemisation
CH3CH == CHC (Br)(CH3)2 can be classified
17. Which of the following alkyl halides will
as ____________.
undergo SN1 reaction most readily?
(i) Allyl
(i) (CH3)3C—F
(ii) Aryl (ii) (CH3)3C—Cl
(iii) Vinyl (iii) (CH3)3C—Br
(iv) (CH3)3C—I
(iv) Secondary 18.
13. Chlorobenzene is formed by reaction of
chlorine with benzene in the presence of AlCl3.
Which of the following species attacks the
benzene ring in this reaction ?
(i) Cl– (i) 1-Bromo-2-ethylpropane
(ii) Cl+ (ii) 1-Bromo-2-ethyl-2-methyl ethane
(iii) AlCl3
(iii) 1-Bromo-2-methylbutane
(iv) [AlCl4]–
14. Ethylidene chloride is a/an ______________. (iv) 2-Methyl-1-bromobutane
(i) vic-dihalide 19. What should be the correct IUPAC name for
diethyl bromomethane?
(ii) gem-dihalide
(i) 1-Bromo-1,1-diethoxyethane
(iii) allylic halide
(ii) 3-Bromopentane
(iv) vinylic halide
(iii) 1-Bromo-1-ethyl propane
(iv) 1-Bromopentane
20. The reaction of toluene with chlorine in the
presence of iron and in the absence of light
 JMD ੴ

yields ____________. by OH– ion?

(i) (a)
(ii) (a), (b), (c)
(iii) (b), (c)
21. Chloromethane on treatment with excess of
(iv) (a), (c)
ammonia yields mainly
Note : In the questions 26 to 29 arrange the
compounds in increasing order of rate of
reaction towards nucleophilic substitution
26.

22. Molecules whose mirror image is non

superimposable over them are known as chiral.
Which of the following molecules is chiral in
nature?
(i) (a) < (b) < (c)
(i) 2-Bromobutane
(ii) (c) < (b) < (a)
(ii) 1-Bromobutane
(iii) (a) < (c) < (b)
(iii) 2-Bromopropane
(iv) (c) < (a) < (b)
(iv) 2-Bromopropan-2-ol
27.
23. Reaction of C6H5CH2Br with aqueous sodium
hydroxide follows ____________.
(i) SN1 mechanism
(ii) SN2 mechanism
(iii) Any of the above two depending upon the
temperature of reaction (i) (a) < (b) < (c)
(iv) Saytzeff rule (ii) (a) < (c) < (b)
24. Which of the carbon atoms present in the (iii) (c) < (b) < (a)
molecule given below are asymmetric (iv) (b) < (c) < (a)
28.

(i) a, b, c, d
(ii) b, c
(iii) a, d (i) (c) < (b) < (a)

(iv) a, b, c (ii) (b) < (c) < (a)

25. Which of the following compounds will give (iii) (a) < (c) < (b)
racemic mixture on nucleophilic substitution (iv) (a) < (b) < (c)
29.
 JMD ੴ
(i) (a) < (b) < (c)
(ii) (b) < (a) < (c)
(iii) (c) < (b) < (a)
(iv) (a) < (c) < (b)
30. Which is the correct increasing order of boiling
points of the following compounds?
1-Iodobutane, 1-Bromobutane, 1-
Chlorobutane, Butane
(i) Butane < 1-Chlorobutane < 1-Bromobutane
< 1-Iodobutane
(ii) 1-Iodobutane < 1-Bromobutane < 1-
Chlorobutane < Butane
(iii) Butane < 1-Iodobutane < 1-Bromobutane
< 1-Chlorobutane
(iv) Butane < 1-Chlorobutane < 1-Iodobutane <
1-Bromobutane
31. Which is the correct increasing order of boiling
points of the following compounds?
1-Bromoethane, 1-Bromopropane, 1-
Bromobutane, Bromobenzene
(i) Bromobenzene < 1-Bromobutane < 1-
Bromopropane < 1-Bromoethane
(ii) Bromobenzene < 1-Bromoethane < 1-
Bromopropane < 1-Bromobutane
(iii) 1-Bromopropane < 1-Bromobutane < 1-
Bromoethane < Bromobenzene
(iv) 1-Bromoethane < 1-Bromopropane < 1-
Bromobutane < Bromobenzene
Multiple Choice Questions (Type-II)
Note : In the following questions two or
more options may be correct. Consider the
following reaction and answer the questions
no. 32–34.
32. Which of the statements are correct about
above reaction?
▪ (i) (a) and (e) both are nucleophiles.
▪ (ii) In (c) carbon atom is sp3 hybridised.
▪ (iii) In (c) carbon atom is sp2 hybridised.
▪ (iv) (a) and (e) both are electrophiles.
33. Which of the following statements are correct
about this reaction?
▪ (i) The given reaction follows SN2 mechanism.
▪ (ii) (b) and (d) have opposite configuration.
▪ (iii) (b) and (d) have same configuration.
▪ (iv) The given reaction follows SN1
mechanism.
34. Which of the following statements are correct
about the reaction intermediate?
▪ (i) Intermediate (c) is unstable because in this
carbon is attached to 5 atoms.
▪ (ii) Intermediate (c) is unstable because carbon
atom is sp2 hybridised.
▪ (iii) Intermediate (c) is stable because carbon
atom is sp2 hybridised.
▪ (iv) Intermediate (c) is less stable than the
reactant (b).
Answer Q. No. 35 and 36 on the basis of the
following reaction.
35. Which of the following statements are correct
about the mechanism of this reaction?
▪ (i) A carbocation will be formed as an
intermediate in the reaction.
▪ (ii) OH– will attach the substrate (b) from one
side and Cl– will leave it simultaneously from
other side.
▪ (iii) An unstable intermediate will be formed in
which OH– and Cl– will be attached by weak
bonds.
▪ (iv) Reaction proceeds through
SN1 mechanism.
36. Which of the following statements are correct
about the kinetics of this reaction?
 JMD ੴ
▪ (i) The rate of reaction depends on the
concentration of only (b).
▪ (ii) The rate of reaction depends on
concentration of both (a) and (b).
▪ (iii) Molecularity of reaction is one.
▪ (iv) Molecularity of reaction is two.
37. Haloalkanes contain halogen atom (s) attached
to the sp3 hybridised carbon atom of an alkyl
group. Identify haloalkane from the following
compounds.
▪ (i) 2-Bromopentane
▪ (ii) Vinyl chloride (chloroethene)
▪ (iii) 2-chloroacetophenone
▪ (iv) Trichloromethane
38. Ethylene chloride and ethylidene chloride are
isomers. Identify the correct statements.
▪ (i) Both the compounds form same product on
treatment with alcoholic KOH.
▪ (ii) Both the compounds form same product on
treatment with aq.NaOH.
▪ (iii) Both the compounds form same product on
reduction.
▪ (iv) Both the compounds are optically active.
39. Which of the following compounds are gem-
dihalides?
▪ (i) Ethylidene chloride
▪ (ii) Ethylene dichloride
▪ (iii) Methylene chloride
▪ (iv) Benzyl chloride
40. Which of the following are secondary
bromides?
▪ (i) (CH3)2 CHBr
▪ (ii) (CH3)3C CH2Br
▪ (iii) CH3CH(Br)CH2CH3
▪ (iv) (CH3)2CBrCH2CH3
41. Which of the following compounds can be
classified as aryl halides?
▪ (i) p-ClC6H4CH2CH(CH3)2
▪ (ii) p-CH3CHCl(C6H4)CH2CH3
▪ (iii) o-BrH2C-C6H4CH(CH3)CH2CH3
▪ (iv) C6H5-Cl
42. Alkyl halides are prepared from alcohols by
treating with
▪ (i) HCl + ZnCl2
▪ (ii) Red P + Br2
▪ (iii) H2SO4 + KI
▪ (iv) All the above
43. Alkyl fluorides are synthesised by heating an
alkyl chloride/bromide in presence of
____________ or ____________.
▪ (i) Ca F2
▪ (ii) CoF2
▪ (iii) Hg2F2
▪ (iv) NaF
Short Answer Type Questions
1. Aryl chlorides and bromides can be easily
prepared by electrophilic substitution of arenes
with chlorine and bromine respectively in the
presence of Lewis acid catalysts. But why does
preparation of aryl iodides requires presence of
an oxidising agent?
2. Out of o-and p-dibromobenzene which one has
higher melting point and why?
3. Which of the compounds will react faster in
SN1 reaction with the –OH ion?
4. Why iodoform has appreciable antiseptic
property?
5. Haloarenes are less reactive than haloalkanes
and haloarenes. Explain.
6. Discuss the role of Lewis acids in the
preparation of aryl bromides and chlorides in
the dark.
7. Which of the following compounds (a) and (b)
will not react with a mixture of NaBr and
H2SO4. Explain why?
8. Which of the products will be major product in
the reaction given below? Explain.
 JMD ੴ
9. Why is the solubility of haloalkanes in water
very low?
10. Draw other resonance structures related to the
following structure and find out whether the
functional group present in the molecule is
ortho, para directing or meta directing.
11. Classify the following compounds as primary,
secondary and tertiary halides.
▪ (i) 1-Bromobut-2-ene
▪ (ii) 4-Bromopent-2-ene
▪ (iii) 2-Bromo-2-methylpropane
12. Compound ‘A’ with molecular formula C4H9Br
is treated with aq. KOH solution. The rate of
this reaction depends upon the concentration of
the compound ‘A’ only. When another
optically active isomer ‘B’ of this compound
was treated with aq. KOH solution, the rate of
reaction was found to be dependent on
concentration of compound and KOH both.
(i) Write down the structural formula of both
compounds ‘A’ and ‘B’.
(ii) Out of these two compounds, which one
will be converted to the product with inverted
configuration.
13. Write the structures and names of the
compounds formed when compound ‘A’ with
molecular formula, C7H8 is treated with Cl2 in
the presence of FeCl3.
14. Identify the products A and B formed in the
following reaction :
(a) CH3 — CH2 — CH == CH — CH3 + HCl
→A+B
15. Which of the following compounds will have
the highest melting point and why?
16. Write down the structure and IUPAC name for
neopentyl bromide.
17. A hydrocarbon of molecular mass 72 g mol–
1
gives a single monochloro derivative and two
dichloro derivatives on photo chlorination.
Give the structure of the hydrocarbon.
18. Name the alkene which will yield 1-chloro-1-
methylcyclohexane by its reaction with HCl.
Write the reactions involved.
19. Which of the following haloalkanes reacts with
aqueous KOH most easily? Explain giving
reason.
▪ (i) 1-Bromobutane
▪ (ii) 2-Bromobutane
▪ (iii) 2-Bromo-2-methylpropane
▪ (iv) 2-Chlorobutane
20. Why can aryl halides not be prepared by
reaction of phenol with HCl in the presence of
ZnCl2?
21. Which of the following compounds would
undergo SN1 reaction faster and why?
22. Allyl chloride is hydrolysed more readily than
n-propyl chloride. Why?
23. Why is it necessary to avoid even traces of
moisture during the use of a Grignard reagent?
24. How do polar solvents help in the first step in
SN1 mechanism?
25. Write a test to detect the presence of double
bond in a molecule.
26. Diphenyls are potential threat to the
environment. How are these produced from
aryl halides?
27. What are the IUPAC names of the insecticide
DDT and benzene hexachloride? Why is their
use banned in India and other countries?
28. Elimination reactions (especially β-
elimination) are as common as the nucleophilic
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substitution reaction in case of alkyl halides. 3. Match the structures of compounds given in
Specify the reagents used in both cases. Column I with the classes of compounds given
in Column II.
29. How will you obtain monobromobenzene from
aniline?
30. Aryl halides are extremely less reactive
towards nucleophilic substitution. Predict and
explain the order of reactivity of the following
compounds towards nucleophilic substitution:

4. Match the reactions given in Column I with the

types of reactions given in Column II.

31. tert-Butyl Bromide reacts with aq. NaOH by

SN1 mechanism while n-butyl bromide reacts
by SN2 mechanism. Why?
32. Predict the major product formed when HCl is
added to isobutylene. Explain the mechanism
involved.
33. Discuss the nature of C–X bond in the
haloarenes.
34. How can you obtain iodoethane from ethanol
when no other iodine containing reagent except
NaI is available in the laboratory?
35. Cyanide ion acts as an ambident nucleophile.
From which end it acts as a stronger
nucleophile in aqueous medium? Give reason
for your answer

Matching Type Questions 5. Match the structures given in Column I with

Note : Match the items given in Column I the names in Column II.
and Column II in the following questions.
1. Match the the compounds given in Column I
with the effects given in Column II.

2. Match the items of Column I and Column II.

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6. Match the reactions given in Column I with the
names given in Column II.
Assertion and Reason Questions
Note : In the following questions a statement
of assertion followed by a statement of
reason is given. Choose the correct answer
out of the following choices.
(i) Assertion and reason both are correct and
reason is correct explanation of assertion.
(ii) Assertion and reason both are wrong
statements.
(iii) Assertion is correct but reason is wrong
statement.
(iv) Assertion is wrong but reason is correct
statement.
(v) Assertion and reason both are correct
statements but reason is not correct explanation
of assertion.
1. Assertion : Phosphorus chlorides (tri and
penta) are preferred over thionyl chloride for
the preparation of alkyl chlorides from
alcohols.
Reason : Phosphorus chlorides give pure alkyl
halides.
2. Assertion : The boiling points of alkyl halides
decrease in the order : RI > RBr > RCl > RF
Reason : The boiling points of alkyl chlorides,
bromides and iodides are considerably higher
than that of the hydrocarbon of comparable
molecular mass.
3. Assertion : KCN reacts with methyl chloride to
give methyl isocyanide
Reason : CN– is an ambident nucleophile.
4. Assertion : tert-Butyl bromide undergoes
Wurtz reaction to give 2, 2, 3, 3-
tetramethylbutane.
Reason : In Wurtz reaction, alkyl halides react
with sodium in dry ether to give hydrocarbon
containing double the number of carbon atoms
present in the halide.
5. Assertion : Presence of a nitro group at ortho or
para position increases the reactivity of
haloarenes towards nucleophilic substitution.
Reason : Nitro group, being an electron
withdrawing group decreases the electron
density over the benzene ring.
6. Assertion : In mono haloarenes, further
electrophilic substitution occurs at ortho and
para positions.
Reason : Halogen atom is a ring deactivator.
7. Assertion : Aryl iodides can be prepared by
reaction of arenes with iodine in the presence
of an oxidising agent.
Reason : Oxidising agent oxidises I2 into HI.
8. Assertion : It is difficult to replace chlorine by
–OH in chlorobenzene in comparison to that in
chloroethane.
Reason : Chlorine-carbon (C—Cl) bond in
chlorobenzene has a partial double bond
character due to resonance.
9. Assertion : Hydrolysis of (–)-2-bromooctane
proceeds with inversion of configuration.
Reason : This reaction proceeds through the
formation of a carbocation.
10. Assertion : Nitration of chlorobenzene leads to
the formation of m-nitrochlorobenzene
Reason : —NO2 group is a m-directing group.
Long Answer Type Questions
1. Some alkyl halides undergo substitution
whereas some undergo elimination reaction on
treatment with bases. Discuss the structural
features of alkyl halides with the help of
examples which are responsible for this
difference.
2. Some halogen containing compounds are
useful in daily life. Some compounds of this
class are responsible for exposure of flora and
fauna to more and more of UV light which
causes destruction to a great extent. Name the
class of these halo compounds. In your
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opinion, what should be done to minimise
harmful effects of these compounds.
3. Why are aryl halides less reactive towards
nucleophilic substitution reactions than alkyl
halides? How can we enhance the reactivity of
aryl halides?
ANSWERS
I. Multiple Choice Questions (Type-I)
1. (ii) 2. (iv) 3. (i) 4. (ii) 5. (i) 6. (i) 7. (i) 8.
(iii), boiling point of (a) 364 K. boiling point of
(b) 375 K, boiling point of (c) 346 K 9. (ii) 10.
(i) 11. (ii) 12. (i) 13. (ii) 14. (ii) 15. (iii) 16. (ii)
17. (iv) 18. (iii) 19. (ii) 20. (iv) 21. (iii) 22. (i)
23. (i) 24. (ii) 25. (i) 26. (iii) 27. (iv) 28. (iv)
29. (iii) 30. (i) 31. (iv)
II. Multiple Choice Questions (Type-II)
32. (i), (iii) 33. (i), (ii) 34. (i), (iv) 35. (i), (iv)
36. (i), (iii) 37. (i), (iv) 38. (i), (iii) 39. (i), (iii)
40. (i), (iii) 41. (i), (iv) 42. (i), (ii) 43. (ii), (iii)
III. Short Answer Type
44. Iodination reactions are reversible in
nature. To carry out the reaction in the forward
direction, HI formed during iodination is
removed by oxidation. HIO4 is used as an
oxidising agent.
45. p-Dibromobenzene has higher melting
point than its o-isomer. It is due to symmetry
of p-isomer which fits in crystal lattice better
than the o-isomer.
46. C6H5—CH2—Cl
47. Due to liberation of free iodine.
50. (b), C—O bond is more stable in (b)
because of resonance.
51. ‘B’ is major product of the reaction.
53. Ortho-para directing due to increase in the
electron density at ortho and para positions.
54. (i) Primary (ii) Secondary (iii) Tertiary
55. (ii) Compound ‘B’.
56. (i) (ii)
57. (A) (B)
58. II, due to symmetry of para-positions; it fits
into crystal lattice better than other isomers.
59. 1-Bromo-2,2-dimethylpropane
62. (iii); The tertiary carbocation formed in the
reaction is stable.
63. C—O bond in phenols is more stable due to
resonance effect and it has double bond
character, hence breaking of this bond is
difficult.
64. (B) Undergoes SN 1 reaction faster than
(A) because in case of (B), the carbocation
formed after the loss of Cl – is stabilised by
resonance, whereas, no such stabilisation is
possible in the carbocation obtained from (A).
65. Allyl chloride shows high reactivity as the
carbocation formed by hydrolysis is stabilised
by resonance while no such stabilisation of
carbocation exists in the case of n-propyl
chloride.
66. Grignard reagents are highly reactive and
react with water to give corresponding
hydrocarbons. RMgX + H2O → RH +
Mg(OH)X
67. Solvation of carbocation
68. (1) Unsaturation test with Br2 water (2)
Bayer’s test
73. III > II > I
76. Discuss polar nature and stabilisation of
C—X bond.
78. It acts as a stronger nucleophile from the
carbon end because it will lead to the formation
of C–C bond which is more stable than the C–
N bond.
IV. Matching Type
79. (i) → (c) (ii) → (d) (iii) → (a) (iv) → (b)
80. (i) → (c) (ii) → (e) (iii) → (a) (iv) → (b)
(v) → (d) 81. (i) → (b) (ii) → (d) (iii) → (a)
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(iv) → (c) 82. (i) → (b) (ii) → (d) (iii) → (e)
(iv) → (a) (v) → (c) 83. (i) → (a) (ii) → (c)
(iii) → (b) (iv) → (d) 84. (i) → (b) (ii) → (a)
(iii) → (d) (iv) → (c)
V. Assertion and Reason Type
85. (ii) 86. (v) 87. (iv) 88. (i) 89. (i) 90. (v) 91.
(iii) 92. (i) 93. (iii) 94. (iv)
VI. Long Answer Type
95. Primary alkyl halides prefer to undergo
substitution reaction by SN2 mechanism
whereas tertiary halides undergo elimination
reaction due to the formation of stable
carbocation.
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CHAPTER

11 ALCOHOLS PHENOLS AND ETHERS

In phenols, -OH group is attached to sp2 hybridized carbon of an aromatic ring. The carbon-oxygen bond
length in phenol is slightly less than alcohol due to partial double bond characters and carbon is sp2
hybridized in alcohols whereas in alcohols, its sp3.

METHODS OF PREPERATION (ALCOHOLS)

1. FROM ALKENES: -
• By Acid Catalyzed Hydration: -

Alkenes react with water in the presence of H2SO4 as catalyst to form alcohols in case of unsymmetrical
alkenes, the addition reaction takes place according to MARKONIKOV’S STYLE.

• By Hydroboration-Oxidation: -

From alkenes we can prepare 1° Alcohol (Anti Markonikov Style) in the presence of diborane,
hydrogrn peroxide and tetra hydrofuran.
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2.FROM GRIGNARD REAGENT: - (Step up reaction)

We can prepare 1°,2° and 3° Alcohols From Grignard reagents but all have Increased no. of carbon
atoms (step up reaction).
• Methanal + Grignard reagents 1° Alcohol
• Expect methanol any aldehyde + G.R 2° Alcohol
• Any ketones +G.R 3° Alcohol

3. FROM CARBONYL GROUPS: - (reduction)

Reduction of aldehydes and Ketones:

(a) Hydrogen gets added in the presence of a catalyst (catalytical hydrogenation) like Pd, Pt, Ni (all
finely. divided)
(b) By treating carbonyl compounds with sodium borohydride or lithium aluminum hydride (Li
AlH4).

Lithium aluminum hydride is stronger reducing agent which reduces carboxylic acids, amides, esters,
ketones and aldehydes while Sodium borohydride reduces only aldehydes and ketones

Aldehydes 1°Alcohol
Ketones 2°Alcohol
Carboxylic Acid 1°Alcohol

➢ PREPERATION OF PHEOLS (Aromatic Alcohols)

1. DOW’S PROCESS (INDUSTRIAL METHOD)

Chlorobenzene is fused with NaOH (at 623 K and 320 atm pressure) to produce sodium phenoxide,
which gives phenol on acidification.
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2. FROM BENZENE DIAZONIUM CHLORIDE

3. FROM BENZENE SULPHONIC ACID

4. FROM CUMENE :

➢ PHYSICAL PROPERTIES

M.P And B.P is directly proportional to molecular mass as by increasing molecular mass, Van der
Waals forces increase while with increasing branching, these forces decrease hence, branching is
inversely proportional to M.P.
Solubility decreases with increase in hydrophobic part i.e., carbon chain

NOTE:- Both M.P. and B.P. and solubility of alcohols have higher than their corresponding
hydrocarbons, ethers , haloalkanes, aldehydes, ketones and amino due to extensive hydrogen bonding it
can from but has lesser values than carboxylic acids.

➢ CHEMICAL PROPERTIES

Alcohols are very versatile in nature due to the polarity in both C-O and O-H bond. They can act as both
nucleophiles and electrophones depending on the site of cleavage.
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Reactions involving the cleavage of O-H bond (i.e. alcohols acts as nucleophiles)

1. REACTION WITH METALS: - (ACIDITY)

Alcohols and phenols react with active metals like sodium and potassium to yield corresponding
alkoxides and phenoxides respectively.

2R O H + 2Na 2R O Na + H₂

The above reactions show the acidic behavior of alcohols and phenols.

Phenols are greater acidic than aliphatic alcohols as after loosing H ⁺, the remaining phenoxide ion can
be stabilized through resonance while such resonance is not possible in alkoxide ions.

• Although there is also charge delocalization (resonance) in phenol but due to the presence of both
positive and negative charges it has charge separation for which the resonating structures of phenol
molecule is less stable than phenoxide ion.
• Presence of EWG (Electron withdrawing group) at ortho and para positions increases the acidity of
phenols as EWG conduct – I effects which increases the polarity of O-H bond and makes the
Ionization easy while EDG conducts +I effect and decreases the bond polarity so , decreases the
acidity.
➢ NOTE : Pka is inversely proportional to Ka it means for strong acids, Ka value is large and PKa
value is less.

Compound Formula pKa

o-Nitrophenol o-O2N-C6H4-OH 7.2

m-Nitrophenol m-O2N-C6H4-0H 8.3

p-Nitrophenol p-O2N-C6H4-0H 7.1

Phenol C6H5-OH 10.0

o-Cresol o-CH3-C6H4-OH 10.2

m-Cresol m-CH3C6H4-OH 10.1

p-Cresol p-CH3-C6H4-OH 10.2

Ethanol C2H5OH 15.9

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2. ESTERIFICATION: -

Alcohols when reacts with carboxylic acids in the presence of conc. H₂ SO₄ it forms sweet smelling
compounds called esters. The reaction with Carboxylic Acid is a reversible reaction so, water is removed
as soon formed. The rate of Esterification decreases with increase in no. of alkyl part

➢ Reactions involving the cleavage of C-O bond (alcohols acts like elctrophiles)

1. Reaction with H-X (Lucas Test)

R OH + HX R -X + H₂O

2. DEHYDRATION: -
• At 443K, (High temperature) the removal of H₂O takes place from single molecule of alcohol, thus
forms alkenes.
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• At 413K, comparatively low temperature) the removal of H₂O takes place from two molecules of
alcohol, thus forms ethers.

3. OXIDATION: -
• Depending on the type of oxidizing agent, a primary alcohol oxidizes to Aldehyde (on mild
oxidation) while oxidizes to a carboxylic acid ( on strong oxidation)
• A 2⁰ alcohol on mild oxidation produces ketone while on vigorous oxidation gives mixture of
carboxylic acid.
• A 3⁰ alcohol does not oxidize while on vigorous oxidation produces alkenes as elimination occurs.

REACTIONS OF PHENOLS
Phenols are the organic compounds containing benzene ring bonded to a hydroxyl group. They are
also known as carbolic acids. Phenols react with active metals like sodium, potassium to form
phenoxide. This reaction of phenol with metals indicates its acidic nature.

Electrophilic Aromatic Substitution Reaction.

The O-H group, attached to benzene ring activates it towards electrophilic substitution reaction and
directs its towards ortho and para positions as due to resonance these positions are very electron rich
due to the delocalization of -ve charge.
The acidity of phenols is due to its ability to lose hydrogen ion to form phenoxide ions.

• Thus, the phenoxide ion is formed. The phenoxide ion formed is stabilized by the delocalization of
negative charge due to the resonance in the benzene ring.
• Phenoxide ion has greater stability than phenols, as in the case of phenol charge separation takes
place during resonance.

Existence of electron attracting group, (for example -NO2, -X, - NR+3, -CN, -CHO, -COOH) on the
benzene ring increases the acidity of phenol since it enables the ring to draw much more electrons from
the phenoxy oxygen and so releasing easily the proton.
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1. NITRATION: -

With dilute, HNO₃ it produces a mixture of ortho and para Nitrophenols, among which a Nitro phenols
are steam volatile due to Intramolecular H –bonding (within the molecule) while p- Nitrophenols are
less steam volatile due to the Intermolecular H-Bonding association of a type of polymeric chains and
thus can easily be separated out

With conc. HNO₃ , it produces 2,4,6 tri nitrophenol (PICRIC ACID)

OH OH

Conc. Sulphuric acid NO₂ – – NO₂

NO₂

2. HALOGENTAION: -
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When phenols are treated with bromine it forms 2,4,6 tri bromo phenol, usually the reaction is carried
out in the presence of FeBr₃ (Halogen carriers) but for phenols, due to the presence of – OH group, they
are already reactive toward electrophilic substitution reaction it’s a white precipitate and hence also used
as a distinguish test for phenols.
While if the reaction is carried out in a low polarity solvent like CHCl₃ (chloroform) and CS₂ (carbon
disulphide) the reaction produces a monosubstituted product as the reactivity of phenol towards
electrophilic substitution reaction is reduced.

3. KOLBE’S REACTION: -

Phenol when reacts with NaOH forms sodium phenoxide which is more reactive towards electrophilic
substitution reaction than even phenol so, when it reacts with CO₂ a weak electrophile to produce ortho
–hydroxybenzoic acid (SALICYLIC ACID).

When salicylic acid is reacted with CH₃COCl (ethonyl chloride) or (CH₃CO)₂O (acetic anhydride) an
ACETYL group (COCH₃) is introduced at ortho position and forms o- acetoxy benzoic acid (ASPIRIN)

4. RIEMER TIEMANN REACTION: -

When a activated sodium phenoxide is treated with a weak electrophile CHCl₃ followed by the reaction
with NaOH and hydrolysis, o- hydroxy benzaidehyde is formed (SALICYLDEHYDE)

• Test of Phenol:
(i) Phenol turns blue litmus to red.
(ii) Aqueous solution of phenol gives a violet colour with a drop of ferric chloride.
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(iii) Phenol gives Liebermann 's nitroso test.

(iv) Aqueous solution of phenol gives a white ppt. of 2,4,6 tribromophenol with bromine water.

• Uses of Phenol :
(a) As an antiseptic in soaps and lotions. "Dettol" (2,4-Dichloro-3,5-dimethyl phenol)
(b) In manufacture of azodyes, phenolphthalein, picric acid (explosive), cyclohexanol (Solvent for
rubber), plastics (bakelite) etc.
(c) In manufacture of drugs like aspirin salol, phenacetin etc.
(d) As preservative for ink.

• Methanol is obtained by the destructive distillation of wood so also known as wood alcohol or wood
spirit. Its poisonous and used to denature ethanol, denatured ethanol is called as methylated spirit.
• Absolute ethanol is mixed with petrol and benzene to use as a motor fuel to generate power and thus
also called as power alcohol.
• Alcohls are also mixed with ethers as a substitute for petrol and refreed as natalite
• The simplest monohydric alcohol, CH3OH, is called carbinol.

➢ ETHERS

The molecule of ether is bent due to lone pair of electron on oxygen atom- bond electron repulsion.
The bond angle is 1100. It is greater than that of water 1050 due to the repulsion between bulky alkyl
groups. Due to bent structure, it posses dipole moment and hence are polar molecules.
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METHODS OF PREPARATION:-

1. BY DEHYDRATION OF ALCOHOLS:-

This method is suitable for the preparation of 1⁰ ethers (primary) otherwise, for alkyl groups, they causes
hindrome and forms alkenes.

2. WILLIAMSONS’S SYNTHESIS:-

Through this method we can prepare, symmetrical as well as unsymmetrical ethers. Also, we can
prepare, 1⁰,2⁰, or 3⁰ ethers. In this method, an alkyl halide is allowed to react with sodium alkoxide.

R – X + R –O Na R – O – R + NaX
This Reaction involves SN₂ attack of an alkoxide ion can primary Halide.

But it has one limitation i.e. we can’t prepare a 3⁰ ether from a 3⁰ haloalkane as a 3⁰ haloalkane yields
an alkenes because in case of secondary and tertiary haloalkanes elimination completes over substitution
reaction.

• Williamson ether synthesis is a laboratory method to prepare symmetrical and unsymmetrical ethers
by allowing alkyl halides to react with sodium alkoxides.

Where alkyl part of haloalkanes is smaller than alkyl part of sodium alkoxide.

• This reaction involves SN2 attack of the alkoxide ion on the alkyl halide. Better results are obtained
in case of primary alkyl halides.

PHYSICAL PROPERTIES
• The C-O Bonds in ethers are polar and thus they have some dipole moment.
• The weak polarity of ethers do not appreciable affect their B.P ethers have much less B.P than
Alcohols due to the inability of forming H-Bonds.
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• While ethers can form h- bonding with water so, its quite soluble and miscible with water

CHEMICAL PROPERTIES

Due to the presence of the lone pairs of electrons on the oxygen atom, ethers behave as a lewis bases.
They dissolve in acids to form oxonium salts.

In aromatic ethers, alkoxy group is a ortho and para directing but it’s less reactive than –OH group.

1. REACTION WITH ALKYL HALIDE

R—O –R’ + H – X R – X + R’ - OH , WHEN (R< R¹)

The reactivity of hydrogen halide is HI > H- Br> H-Cl due to large in size the cleavage becomes easy.

2. Electrophilic substitution in alkyl aryl ethers

The alkyl group (-OR) is ortho, para directing and activates the aromatic ring towards electrophilic
substitution in the same way as in phenol.
The resonating structures are shown below.

(i) Halogenation
Phenyl alkyl ethers undergo usual halogenation in the benzene ring.
For e.g., Anisole undergoes bromination with Br2 in ethanoic acid even in absence of Iron (III) bromide
catalyst.

As the benzene ring is activated by methoxy group, the reaction occurs as such. Para isomer is obtained
in 90% yield.

(ii) Fridel Craft's reaction

Anisole undergoes Friedel craft's reaction with alkyl halide and aryl halide in presence of Aluminium
chloride (a Lewis acid) as catalyst.
The alkyl and aryl groups are introduced at ortho and para positions.

➢ Uses of ether :
(i) General anaesthetics agent.
(ii) Refrigerant a mixture of ether and dry ice gives temperature as low 110°C.
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(iii) Solvent for oil, fats, resins, Grignard reagent.

(iv) For providing inert & moist free medium to organic reaction example : Wurtz reactions.
(v) In perfumery.
(vi) Di-isopropyl ether Petrol as an antiknock comp.
(vii) Mixture of alcohol and ether is used as a substitute of petrol. Trade name "Natalite"

➢ SOME IMPORTANT LINES FROM NCERT

• For naming polyhydric alcohols, the ‘e’ of alkane is retained and the ending ‘ol’ is added.
Ex. HO–H2C–CH2–OH (Ethylene glycol) Ethane-1,2-diol.
• The bond angle in alcohols is slightly less than the tetrahedral angle (109°). It is due to the repulsion
between the unshared electron pairs of oxygen.
• The carbon– oxygen bond length (136 pm) in phenol is slightly less than that in methanol due to
partial double bond character.
• The bond angle in ethers is slightly greater than the tetrahedral angle due to the repulsive interaction
between the two bulky (–R) groups.
• Carboxylic acids are reduced to primary alcohols in excellent yields by lithium aluminium hydride,
a strong reducing agent. However, LiAlH4 is an expensive reagent, and therefore, used for preparing
special chemicals only. Commercially, acids are reduced to alcohols by converting them to the esters
(esterification) followed by their reduction using hydrogen in the presence of nickel.
• Phenol, also known as carbolic acid.
• The boiling points of alcohols and phenols increase with increase in the number of carbon atoms
due to increase in van der Waals forces. In alcohols, the boiling points decrease with increase of
branching in carbon chain because of decrease in van der Waals forces with decrease in surface area.
• It is interesting to note that boiling points of alcohols and phenols are higher in comparison to
hydrocarbons, ethers, haloalkanes and haloarenes of comparable molecular masses.it’s due to the
presence of intermolecular hydrogen bonding
• Solubility of alcohols and phenols in water is due to their ability to form hydrogen bonds with water
molecules.
• Alcohols are versatile compounds. They react both as nucleophiles and electrophiles. The bond
between O–H is broken when alcohols react as nucleophiles while if the bond between C–O is
broken they react as electrophiles.
• The acidic character of alcohols is due to the polar nature of O–H bond. An electron-releasing group
(–CH3, –C2H5 decreases the acid strength. Alcohols are, however, weaker acids than water.
• Phenols are more acidic than aliphatic alcohols as after the removal of proton the remaining
phenoxide ion is resonance stabilized. In substituted phenols, the presence of electron withdrawing
groups such as nitro group, enhances the acidic strength of phenol. This effect is more pronounced
when such a group is present at ortho and para positions. It is due to the effective delocalisation of
negative charge in phenoxide ion than at ortho or para position. On the other hand, electron releasing
groups, such as alkyl groups, in general, do not favour the formation of phenoxide ion resulting in
decrease in acid strength. Cresols, for example, are less acidic than phenol.
• The reaction of alcohols with carboxylic acid and acid anhydride is carried out in the presence of a
small amount of concentrated sulphuric acid. The reaction is reversible, and therefore, water is
removed as soon as it is formed. The reaction with acid chloride is carried out in the presence of a
base (pyridine) so as to neutralise HCl which is formed during the reaction. It shifts the equilibrium
to the right hand side.
• Thus, the relative ease of dehydration of alcohols follows the following order due to stability of
carbocations
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Tertiary > Secondary > Primary

• A primary alcohol is oxidised to an aldehyde which in turn is oxidised to a carboxylic acid.
Strongoxidising agents such as acidified potassium permanganate are used for getting carboxylic
acids from alcohols directly. A better reagent for oxidation of primary alcohols to aldehydes in good
yield is pyridinium chlorochromate (PCC). Secondary alcohols are oxidised to ketones by chromic
anhydride (CrO3).
• Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as strong
oxidising agents (KMnO4) and elevated temperatures, cleavage of various C-C bonds takes place
and a mixture of carboxylic acids containing lesser number of carbon atoms is forme.
• When the vapours of a primary or a secondary alcohol are passed over heated copper at 573 K,
dehydrogenation takes place and an aldehyde or a ketone is formed while tertiary alcohols undergo
dehydration.
• At times the alcoholics, by mistake, drink ethanol, mixed with methanol also called denatured
alcohol. In the body, methanol is oxidised first to methanal and then to methanoic acid, which may
cause blindness and death.
• The –OH group attached to the benzene ring activates it towards electrophilic substitution to ortho
and para positions in the ring as these positions become electron rich due to +R effect.
• With dilute nitric acid at low temperature (298 K), phenol yields a mixture of ortho and para
nitrophenols. The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is
steam volatile due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to
intermolecular hydrogen bonding which causes the association of molecules.

• With concentrated nitric acid, phenol is converted to 2,4,6-trinitrophenol i.e picric acid.

• When the reaction is carried out in solvents of low polarity such as CHCl 3 or CS2 and at low
temperature, monobromophenols are formed. The usual halogenation of benzene takes place in the
presence of a Lewis acid, such as FeBr3 which polarises the halogen molecule. In case of phenol,
the polarisation of bromine molecule takes place even in the absence of Lewis acid. It is due to the
highly activating effect of –OH group attached to the benzene ring.
• When phenol is treated with bromine water 2,4,6-tribromophenol is formed as white precipitate and
used as a distinguish test for phenols.
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• In the presence of air, phenols are slowly oxidised to dark coloured mixtures containing quinones.
• Methanol, CH3OH, also known as ‘wood spirit’, was produced by destructive distillation of wood.
Today, most of the methanol is produced by catalytic hydrogenation of carbon monoxide at high
pressure and temperature and in the presence of ZnO – Cr2O3 catalyst. Methanol is used as a solvent
in paints, varnishes and chiefly for making formaldehyde.

• Ethanol, C2H5OH, is obtained commercially by fermentation. The sugar in molasses, sugarcane or

fruits such as grapes is converted to glucose and fructose, in the presence of an enzyme, invertase.
Glucose and fructose undergo fermentation in the presence of another enzyme, zymase, which is
found in yeast.

• The action of zymase is inhibited once the percentage of alcohol formed exceeds 14 percent. If air
gets into fermentation mixture, the oxygen of air oxidises ethanol to ethanoic acid which in turn
destroys the taste of alcoholic drinks.
• Acidic dehydration of alcohols to give an ether is suitable for the preparation of ethers having
primary alkyl groups only. The alkyl group should be unhindered and the temperature be kept low.
Otherwise the reaction favours the formation of alkene.
• In Williamson’s synthesis of ether better results are obtained if the alkyl halide is primary. In case
of secondary and tertiary alkyl halides, elimination competes over substitution. If a tertiary alkyl
halide is used, an alkene is the only reaction product and no ether is formed. For example, the
reaction of CH3ONa with (CH3)3C–Br gives exclusively 2-methylpropene. It is because alkoxides
are not only nucleophiles but strong bases as well.
• The C-O bonds in ethers are polar and thus, ethers have a net dipole moment.
• The large difference in boiling points of alcohols and ethers is due to the presence of hydrogen
bonding in alcohols.
• The miscibility of ethers with water resembles those of alcohols of the same molecular mass as
oxygen of ether can also form hydrogen bonds with water.
• The cleavage of ethers takes place with concentrated HI or HBr at high temperature. However, when
one of the alkyl group is a tertiary group, the halide formed is a tertiary halide. It is because in the
departure of leaving group (HO–CH3) creates a more stable carbocation [(CH3)3C+],
• The alkoxy group (-OR) is ortho, para directing and activates the aromatic ring towards electrophilic
substitution in the same way as in phenol.
• Anisole undergoes bromination with bromine in ethanoic acid even in the absence of iron (III)
bromide catalyst. It is due to the activation of benzene ring by the methoxy group. Para isomer is
obtained in 90% yield.
JMD ੴ

➢ NOTE Lucas test it is used to distinguish between primary, secondary and tertiary alcohols as tertiary
alcohols gives immediate turbidity with hydrochloric acid while secondary alcohol gives white turbidity
within 5 minutes and primary alcohol gives no turbidity at room temperature while gives turbidity upon
heating. In secondary and primary alcohols anhydrous zinc chloride is needed to facilitate the reaction.
 JMD ੴ
➢ NCERT EXEMPLAR ▪ (ii) A, D
1. Monochlorination of toluene in sunlight ▪ (iii) B, C
followed by hydrolysis with aq. NaOH yields. ▪ (iv) A
▪ (i) o-Cresol 7. Give IUPAC name of the compound given
▪ (ii) m-Cresol below.
▪ (iii) 2, 4-Dihydroxytoluene
▪ (iv) Benzyl alcohol
2. How many alcohols with molecular formula ▪ (i) 2-Chloro-5-hydroxyhexane
C4H10O are chiral in nature?
▪ (ii) 2-Hydroxy-5-chlorohexane
▪ (i) 1
▪ (iii) 5-Chlorohexan-2-ol
▪ (ii) 2
▪ (iv) 2-Chlorohexan-5-ol
▪ (iii) 3
8. IUPAC name of m-cresol is ___________.
▪ (iv) 4
▪ (i) 3-methylphenol
3. What is the correct order of reactivity of
alcohols in the following reaction? ▪ (ii) 3-chlorophenol
▪ (iii) 3-methoxyphenol
▪ (iv) benzene-1,3-diol
▪ (i) 1° > 2° > 3°
9.
▪ (ii) 1° < 2° > 3°
▪ (iii) 3° > 2° > 1°
▪ (iv) 3° > 1° > 2° ▪ (i) 1-methoxy-1-methylethane
4. CH3 CH3 OH2 can be converted into CH3CHO ▪ (ii) 2-methoxy-2-methylethane
by ______________.
▪ (i) catalytic hydrogenation ▪ (iii) 2-methoxypropane

▪ (ii) treatment with LiAlH4 ▪ (iv) isopropylmethyl ether

▪ (iii) treatment with pyridinium chlorochromate 10. Which of the following species can act as the
▪ (iv) treatment with KMnO4 strongest base?
5. The process of converting alkyl halides into
alcohols involves_____________.
▪ (i) addition reaction
▪ (ii) substitution reaction
▪ (iii) dehydrohalogenation reaction
▪ (iv) rearrangement reaction
6. Which of the following compounds is aromatic 11. Which of the following compounds will react
alcohol? with sodium hydroxide solution in water?
▪ (i) C6H5OH
▪ (ii) C6H5CH2OH
▪ (iii) (CH3)3COH
▪ (iv) C2H5OH
▪ (i) A, B, C, D 12. Phenol is less acidic than ______________.

125
 JMD ੴ

▪ (i) ethanol 18. Which of the following are used to convert

RCHO into RCH2OH?
▪ (ii) o-nitrophenol
▪ (i) H2/Pd
▪ (iii) o-methylphenol ▪ (ii) LiAlH4
▪ (iv) o-methoxyphenol ▪ (iii) NaBH4
▪ (iv) Reaction with RMgX followed by
13. Which of the following is most acidic?
hydrolysis
▪ (i) Benzyl alcohol
19. Which of the following reactions will yield
▪ (ii) Cyclohexanol phenol?
▪ (iii) Phenol
▪ (iv) m-Chlorophenol
14. Mark the correct order of decreasing acid
strength of the following compounds.

▪ e>d>b>a>c
▪ b>d>a>c>e
▪ d>e>c>b>a
▪ e>d>c>b>a
15. Mark the correct increasing order of reactivity
of the following compounds with HBr/HCl. 20. Which of the following reagents can be used to
oxidise primary alcohols to aldehydes?
▪ CrO3 in anhydrous medium.
▪ KMnO4 in acidic medium.
▪ Pyridinium chlorochromate.
▪ Heat in the presence of Cu at 573K.
21. Phenol can be distinguished from ethanol by
16. Arrange the following compounds in the reactions with _________.
increasing order of boiling point. Propan-1-ol,
▪ (i) Br2/water
butan-1-ol, butan-2-ol, pentan-1-ol
▪ (ii) Na
▪ Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
▪ (iii) Neutral FeCl3
▪ Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol ▪ (iv) All the above
▪ Pentan-1-ol, butan-2-ol, butan-1-ol, propan-1-ol
▪ Pentan-1-ol, butan-1-ol, butan-2-ol, propan-1-ol

Multiple Choice Questions(Type-II)

Note : In the following questions two or more
options may be correct.
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22. Which of the following are benzylic alcohols?
Short Answer Type Questions
1. What is the structure and IUPAC name of
glycerol?
2. Write the IUPAC name of the following
compounds.
3. Write the IUPAC name of the compound given
below.
4. Name the factors responsible for the solubility
of alcohols in water.
5. What is denatured alcohol?
6. Suggest a reagent for the following conversion.
7. Out of 2-chloroethanol and ethanol which is
more acidic and why?
8. Suggest a reagent for conversion of ethanol to
ethanal.
9. Suggest a reagent for conversion of ethanol to
ethanoic acid.
10. Out of o-nitrophenol and p-nitrophenol, which
is more volatile? Explain.
11. Out of o-nitrophenol and o-cresol which is
more acidic?
12. When phenol is treated with bromine water,
white precipitate is obtained. Give the structure
and the name of the compound formed.
13. Arrange the following compounds in
increasing order of acidity and give a suitable
explanation. Phenol, o-nitrophenol, o-cresol
14. Alcohols react with active metals e.g. Na, K
etc. to give corresponding alkoxides. Write
down the decreasing order of reactivity of
sodium metal towards primary, secondary and
tertiary alcohols.
15. What happens when benzene diazonium
chloride is heated with water?
16. Arrange the following compounds in
decreasing order of acidity. H2O, ROH, HC ≡
CH
17. Name the enzymes and write the reactions
involved in the preparation of ethanol from
sucrose by fermentation.
18. How can propan-2-one be converted into tert-
butyl alcohol?
19. Write the structures of the isomers of alcohols
with molecular formula C4H10O. Which of
these exhibits optical activity?
20. Explain why is OH group in phenols more
strongly held as compared to OH group in
alcohols.
21. Explain why nucleophilic substitution reactions
are not very common in phenols.
22. Preparation of alcohols from alkenes involves
the electrophilic attack on alkene carbon atom.
Explain its mechanism.
23. Explain why is O==C==O nonpolar while R—
O—R is polar.
24. Why is the reactivity of all the three classes of
alcohols with conc. HCl and ZnCl2 (Lucas
reagent) different?
25. Write steps to carry out the conversion of
phenol to aspirin.
26. Nitration is an example of aromatic
electrophilic substitution and its rate depends
upon the group already present in the benzene
ring. Out of benzene and phenol, which one is
more easily nitrated and why?
27. In Kolbe’s reaction, instead of phenol,
phenoxide ion is treated with carbon dioxide.
Why?
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28. Dipole moment of phenol is smaller than that given in Column II.
of methanol. Why?
29. Ethers can be prepared by Williamson
synthesis in which an alkyl halide is reacted
with sodium alkoxide. Di-tert-butyl ether can’t
be prepared by this method. Explain.
30. Why is the C—O—H bond angle in alcohols
slightly less than the tetrahedral angle whereas
the C—O—C bond angle in ether is slightly
greater?
31. Explain why low molecular mass alcohols are
soluble in water.
32. Explain why p-nitrophenol is more acidic than
phenol.
33. Explain why alcohols and ethers of comparable
molecular mass have different boiling points?
34. The carbon-oxygen bond in phenol is slightly
stronger than that in methanol. Why?
35. Arrange water, ethanol and phenol in
increasing order of acidity and give reason for
your answer.

Matching Type Questions

Note : Match the items of Column I and
Column II in the following questions.

1. Match the structures of the compounds given in

Column I with the name of the compounds

2. Match the starting materials given in Column I

with the products formed by these (Column II)
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in the reaction with HI. Assertion and Reason Type Questions

Note : In the following questions a statement
of assertion followed by a statement of reason
is given. Choose the correct answer out of the
following choices.
(i) Assertion and reason both are correct and
reason is correct explanation of assertion.
(ii) Assertion and reason both are wrong
statements.
(iii) Assertion is correct statement but reason is
wrong statement.
(iv) Assertion is wrong statement but reason is
correct statement.
(v) Both assertion and reason are correct
statements but reason is not correct explanation
of assertion.

1. Assertion : Addition reaction of water to but-1-

ene in acidic medium yields butan-1-ol
Reason : Addition of water in acidic medium
proceeds through the formation of primary
carbocation.
2. Assertion : p-nitrophenol is more acidic than
3. Match the items of column I with items of phenol.
column II. Reason : Nitro group helps in the stabilisation
of the phenoxide ion by dispersal of negative
charge due to resonance.

3.

4. Match the items of column I with items of
column II.
4. Assertion : : Bond angle in ethers is slightly
less than the tetrahedral angle.
Reason : : There is a repulsion between the two
bulky (—R) groups.
5. Assertion : : Boiling points of alcohols and
ethers are high.
Reason : They can form intermolecular
hydrogen-bonding.
6. Assertion : Like bromination of benzene,
bromination of phenol is also carried out in the
presence of Lewis acid.
Reason : Lewis acid polarises the bromine
molecule.
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7. Assertion : o-Nitrophenol is less soluble in
water than the m- and p-isomers.
Reason : m- and p- Nitrophenols exist as
associated molecules.
8. Assertion : Ethanol is a weaker acid than
phenol.
Reason : Sodium ethoxide may be prepared by
the reaction of ethanol with aqueous NaOH.
9. Assertion :: Phenol forms 2, 4, 6 –
tribromophenol on treatment with Br2 in carbon
disulphide at 273K.
Reason : Bromine polarises in carbon
disulphide.
10. Assertion : Phenols give o- and p-nitrophenol
on nitration with conc. HNO3 and
H2SO4mixture.
Reason : —OH group in phenol is o–, p–
directing.
Long Answer Questions
1. Write the mechanism of the reaction of HI with
methoxybenzene.
2. (a) Name the starting material used in the
industrial preparation of phenol.
(b) Write complete reaction for the bromination
of phenol in aqueous and non aqueous
medium.
(c) Explain why Lewis acid is not required in
bromination of phenol?
3. How can phenol be converted to aspirin?
4. Explain a process in which a biocatalyst is used
in industrial preparation of a compound known
to you.
ANSWERS
I. Multiple Choice Questions (Type-I)
1. (iv) 2. (i) 3. (iii) 4. (iii) 5. (ii) 6. (iii) 7. (iii) 8. (i)
9. (iii) 10. (ii) 11. (i) 12. (ii) 13. (iv) 14. (ii) 15. (iii)
16. (i)
II. Multiple Choice Questions (Type-II)
17. (i), (ii), (iii) 18. (i), (ii), (iii) 19. (i), (iii), (iv) 20.
(i), (iii) 21. (ii), (iii)
III. Short Answer Type
22. Propane-1,2,3-triol
23. (A) 3-Ethyl-5-methylhexane-2,4-diol, (B) 1-
Methoxy-3-nitrocyclohexane
24. 3-Methylpent-2-ene-1,2-diol
25. (i) Hydrogen bonding (ii) Size of alkyl/aryl
group.
26. Alcohol is made unfit for drinking by mixing
some copper sulphate and pyridine in it. This is
called denatured alcohol.
28. 2-Chloroethanol, due to –I effect of chlorine
atom.
29. CrO3 , Pyridine and HCl (Pyridinium
chlorochromate)
30. Any strong oxidising agent e.g., acidified
KMnO4 or K2Cr2O7 .
31. Intramolecular hydrogen bonding in o-
nitrophenol and intermolecular hydrogen bonding
in p-nitrophenol
32. o-Nitrophenol as CH3 group is electron
releasing
33. (2, 4, 6- Tribromophenol)
34. Increasing order of acidity : o-cresol < phenol
< o-nitrophenol
In substituted phenols, the presence of electron
withdrawing groups, enhance the acidic strength
of phenol whereas, electron releasing groups
decrease the acidic strength of phenol.] 35.
Decreasing order of reactivity of sodium metal is
: 1° > 2° > 3°
36. It gives phenol
37. H2O > ROH > HC ≡≡CH
39. Using Grignard reagent
45. An alcohol reacts with conc. HCl and ZnCl2
(Lucas reagent) to give carbocation. More stable
is the carbocation, faster is the reaction.
47. Phenol is more easily nitrated than benzene as
the presence of —OH group in phenol increases
the electron density at ortho and para positions in
benzene ring by +R effect. The nitration, being
an electrophilic substitution reaction is more
facile where the electron density is more.
48. Phenoxide ion is more reactive than phenol
towards electrophilic aromatic substitution and
hence undergoes electrophilic substitution with
carbondioxide which is a weak electrophile. 49.
In phenol, C—O bond is less polar due to
electron-withdrawing effect of benzene ring
whereas in methanol, C—O bond is more polar
due to electronreleasing effect of —CH3 group.
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50. In tert-butyl halides, elimination is favoured

over substitution, so alkene is the only reaction
product and ether is not formed.
55. This is due to the fact that— (i) In phenol,
conjugation of unshared electron pair over
oxygen with aromatic ring results in partial
double bond character in carbonoxygen bond. (ii)
In phenol, oxygen is attached to a sp2 hybridised
carbon atom while in methanol, it is attached to a
sp3 hyrbidised carbon atom. The bond formed
between oxygen and sp2 hybridised carbon is
more stable than that formed between oxygen and
sp3 hybridised carbon.
56. Increasing order of acidity is ethanol < water
< phenol. The phenoxide ion obtained after the
removal of a proton is stabilised by resonance
whereas the ethoxide ion obtained after the
removal of a proton is destabilised by ‘+I’ effect
of —C2H5 group. Therefore phenol is stronger
acid than ethanol. On the other hand ethanol is
weaker acid than water because electron releasing
—C2H5 group in ethanol inreases the electron
density on oxygen and hence the polarity of O—
H bond in ethanol decreases which results in the
decreasing acidic strength. Hence acidic strength
increases in the order given above.
IV. Matching Type
57. (i) — (d), (ii) — (c), (iii) — (f), (iv) — (a);
(v) — (g), (vi) — (b) 58. (i) — (d), (ii) — (e),
(iii) — (b), (iv) — (a) 59. (i)—(e), (ii)—(f),
(iii)—(d), (iv)—(c), (v)—(a), (vi)—(b) 60. (i) —
(d), (ii) — (a), (iii) — (f), (iv) — (e); (v) — (c),
(vi) — (b)
V. Assertion and Reason Type
61. (ii) 62. (i) 63. (iv) 64. (iv) 65. (ii) 66. (iv) 67.
(v) 68. (iii) 69. (ii) 70. (iv)
 JMD ੴ
CHAPTER

12 ALDEHYDES KETONES AND CARBOXYLIC ACID

Aldelydes, ketones and carboxylic acids all of them having common is carbonyl group (>C=0) which is the
most important functional group in organic chemistry.

In IUPAC Nomenclature, aldelydes are more prefered than ketones and thus ketones in the presence of
Aldeydes are not regarded as in main parent chain and referred as keto or oxo.

METHODS OF PREPARATION (ALDEHYDES AND KETONES)

1) FROM ALCOHOLS:-

a) Mild oxidation :

Primary alcohols on mild or controlled oxidation gives aldehyde while secondary alcohols produces
ketones.

1⁰ Alcohol Aldehyde 20 Alcohol Ketone

PCC and Jones reagent are mild oxidizing agents widely used for these oxidations.
Pyridinium chlorochromate (PCC; C₅H₅NHCrO₃Cl) can be prepared by mixing pyridine (C₅H₅N),
chromium trioxide (CrO₃) and HCl in 1:1:1 while Jones reagent is a solution of CrO₃, sulphuric acid and
aqueous acetone. It is also known as Corey’s reagent.

b) Dehydrogenation of alcohols with copper at 573K

When vapours of alcohols are passed over reduced copper at 573K it yields aldehydes and ketones.

2) FROM ACID CHLORIDES (ACYL DERIVATIVES) (ROSENMUND REACTION)

Aliphatic and aromatic aldehydes can be prepared by the reduction of acid chlorides with H₂ in the presence
of palladium (Pd) deposited over barium sulphate with small amount of sulphur or quinoline (this mixture
is called as LINDLAR’S CATALYST)

Both sulphur and quinoline poisons palladium to check its ability to reduce aldehyde back into alcohol.
Pd – BaSO4
CH₃COCl + H₂ CH₃CHO + HCl
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3) FROM ALKENES (OZONOLSIS)

Alkenes from ozonides with ozone in an inert solvent like CCl₄. The ozonides are cleaved by zinc dust and
water to give two molecules of aldehydes or ketones.

CCl4 O

CH₂ = CH₂ + O₃ CH₂ CH₂ 2CH₂O 2HCHO

Ethene O O Methanal (Formaldehyde)

4) FROM ALKYNES

Ethyene gets hydrated in the presence of a mixture of dilute H₂SO₄ and mercuric acid(HgSO 4) which
tautomerizes to a more stable compound i.e ethanal while all the other alkynes will give ketones.

5) FROM CYANIDES (STEPHENS REDUCTION) (only aldehydes)

From cyanides, aldehydes can be prepared by Stephen’s Reduction Cyanides are reduced with stannous
chloride in the presence of HCl to form an addition compounds which upon warming with water yield
aldehydes.

SnCl₂ + 2HCl SnCl₄ + 2[H]

2 CH₃CN + 2[H] CH₃ - CH = NH + H₂ O

CH₃ - CHO + NH3

Can also be written as:

SnCl2 + HCl
CH₃ CN CH₃CHO

6) FROM BENZENE: - (GATTERMAN KOCH REACTION) (only aldehydes)

Benzaldehyde can be prepared from benzene by passing vapours of carbon monoxide and hydrochloric acid
in the presence of catalyst mixture AlCl₃ and CuCl.
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7) FROM TOULENE (ETARD REACTION) (only aldehydes)

Oxidation of toluene with chromyl chloride dissolved in CCl₄ yields benzaldehyde

Also benzaldehyde can be prepared by the side chain halogenation of toluene.

8) PREPARATION OF KETONES FROM ACYL CHLORIDES

Acyl chlorides upon treatment with Grignard reagent and a metal halide, yield ketones. For example:
when cadmium chloride is reacted with the Grignard reagent, dialkyl cadmium is formed.
Dialkylcadmium thus formed is further reacted with acyl chlorides to form ketones.

9) PREPARATION OF KETONES FROM NITRILES

Treatment of nitriles with Grignard reagent upon further hydrolysis yields ketones.
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PHYSICAL PROPERTIES

• Methanol is a gas at room temperature and ethanol is a volatile liquid while other higher other
aldehydes and ketones are liquids or solida at room temperature.
• B.P. of aldehydes and ketones are higher than those of corresponding hydrocarbons and ethers which
is due to the weak molecular associations in aldehydes and ketones arising out of the dipole- dipole
interactions But B.p is lower than corresponding alcohols due to the absence of intermolecular
hydrogen-Bonding.
• Lower member of aldehydes and ketones such as methanol, ethanol and proponone are miscible with
water in all proportions as they form hydrogen bond with water.
• However, the solubility of aldehydes and ketones decreases rapidly on increasing the length of alkyl
chain due to the hydrophobicners of hydrocarbon part.
• All aldehydes and ketones are fairly soluble in organic solvants like benzene, chloroform etc.
JMD ੴ

CHEMICAL REACTIONS (ALDEHYDES AND KETONES)

1.) NCUCLEOPHILIC ADDITION REACTIONS

A) With HCN it form cyanohydrins

B) With NaHSO₃ (for purification purposes)
C) With Grignard Reagent
a) HCHO +G.R 1 ̊ alcohol
b) Any other aldehyde except HCHO + G.R 2 ̊ alcohol
c) Ketones + G.R 3 ̊ Alcohol
D) With alcohol
a) Aldehyde + Alcohol Hemi – acetal Acetal
b) Ketones + Alcohol Ketal
E) With Nitrogen Derivative
a) Ammonia Imines
b) Amine Schift’s Base
c) Hydroxylamine Oxime
d) Hydrazine Hydrazone
e) Phenyl Hydrazine Phenyl Hydrazone
f) 2,4 Di Nitro Phenyl Hydrazine 2,4 DNP Derivative
g) Semi- Carbazide Semi- Carbazone

2.) REDUCTION

a) Simple- Reduction ( Reduction To Alcohols)

b) Wolff- Kishner Reduction
c) Clemmensen Reduction

3.) OXIDATION

a) Simple oxidation
b) Tollens ‘test
c) Fehling’s test
d) Iodoform test

4.) REACTIONS DUE TO alpha- HYDROGEN

a) Aldol (alpha hydrogen present)

b) Cannizzaro (alpha hydrogen absent)
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1.) NUCLEOPHILIC ADDITION REACTION

Carbonyl group. in aldehydes and ketones is polar, thus participates in the addition reaction proceed by
nucleophilic mechanism (which means the attaching reagent is a nucleophile (nu) which attacks on carbon
which acts as an electrophile with +ve charge)

Due to the greater electronegativity of oxygen atom, the double bond shifts towards it which makes it
negativily charged while leaves the carbon with positive charge which starts attracting negatively charged
nucleophile.

R – C – H/R + Nu Θ R – C- H/R R – C – H/R

Fast
+ Nuˉ Nu-
The Nucleophilic attack gets accelerated of the medium is weakly acidic in nature i.e. (pH=3.5) under this
condition, the carbonyl group gets protonated thereby making the electrometric effect since the resulting
ions gets resonance stabilized, which makes the attack easier. However strongly acidic medium is not
suitable as the excess of the acid will Protonate Nucleophile as well and its attacking capacity will be
considerably Reduced.

However, Aldehydes one more reactive than Ketones towards Nucleophilic addition reaction due to the
following reasons: -

Steric Reason: - Two bulky Alkyl groups in ketones produces Steric Hindrance (Repulsion) to the
coming Nucleophile.
Electronic Reason: Two bulky groups. (Alkyl groups) Attached to carbon in ketones posses + I effect
due to their electron donating tendancy, it reduces the electrophilicity (+ veness of carbon) and hence,
carbon attracts Nucleophile (-ve) with less power.

Greater the size of alkyl group, greater will be the magnitude of +I conducted by it and hence lesser the
reactivity will be.
Also Aromatic groups. which conducts (-I) effect which should Increase the electrophilicity of carbon and
thus the Reactivity should expected to Increase but decrease as it cause resonance ( delocalization of
charge ) which actually Reduces its Reacting power.Moreover, the bulky aromatic part always hinders the
coming nucleophile.
So, order of Reacting towards Nucleophilic Addition Reaction

METHANAL > ETHANAL > BENZALDEHYDE > PROPANONE > BENZOPHENONE

a. WITH HCN:-

Aldelydes or Ketones reacts with HCN to form cynohydrins (compounds in which alcohols and
cyanide group.attached to the same carbon)
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HCN is a weak acid and the reaction is carried in Basic medium in order to generate CN⁻ in order to
generate CN⁻ ion for the Nucleophilic attack.

b. WITH SODIUM BISULPHITE (NaHSO₃): -

Aldehydes and ketones react with NaHSO₃ to form a white crystalline addition compound, which is
very useful in the purification of Aldehydes and ketones as, impurities do not able to form white
crystalline addition product so, can easily be separated out from non-carbonyl group and also we can
back our pure aldehyde and ketones form addition product by reacting it with HCl or NaOH

c. WITH GRIGNARD REAGENT ( R–Mg–X )( STEP UP REACTION )

Aldehydes and ketones add on with Grignard reagent to form addition products which upon
hydrolysis with water and mineral acids to give alcohols.

d. WITH ALCOHOL (Formation of Acetals and Ketols)

• Aldehydes react with one equivalent of monohydric Alcohol in the presence of dry H-Cl to yield
alkoxyalcohol (called Hemi-acetals, which contains ether and alcohol group. Simultaneously on a
JMD ੴ

same carbon) which further alcohol to give a gem – dialkoxy compound called Acetals (contains
both Alkoxy, ether group. on same carbon.

• Ketones does not reacts with monohydric alcohols and with dihydric alcohols like ethylene glycol
to form cyclic ketals.

• Dry HCl protonates the oxygen of carbonyl compounds and thus, increases the electrophilicity
(+ve) of carbon which increases the Nucleophilic attack of oxygen of ethylene glycol.

e. ADDITION OF AMMONIA AND ITS DERIVATIVE

Nitrogen nucleophiles such as ammonia and its derivatives H2N - Z add to carbonyl group of aldehydes
and ketones. The reaction is reversible and catalyszed by acid. The equilibrium favors the product
formation due to rapid dehydration of the tetrahedral addition product.

The net result is replacement of the >C = O group with >C = N - Z group.

• Aldehydes and ketones react with primary amines to form Schiff's base or imines.

• Aldehydes and ketones react with hydrazine to form hydrazones.

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• Aldehydes and ketones react with hydroxylamine to form oximes.

The oximes can be hydrolyzed back to aldehydes and ketones by reaction with acids.

• Aldehydes and ketones react with 2,4-dinitrophenyl hydrazine to form

2,4dinitrophenylhydrazones commonly known as DNP or Brady's reagent.

2,4-DNP derivatives are yellow, orange or red solids useful for characterization test of
aldehydes and ketones.

• Ammonia also reacts with aldehydes (except formaldehyde) and ketones to form the
products called imines.

However formaldehyde reacts with ammonia to form hexamethylene tetramine (CH2)6N4 also
known asurotropine.

Urotropine is used as a medicine to treat urinary infections. Nitration of urotropine under

controlled condition gives an explosive RDX (Research and development explosive).
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• With semicarbazide (NH2 – NHCONH2)

In semi carbazide there are 2 amino group. (-NH₂) but only one undergoes reaction as the other amino
group is indulged on showing resonance with the carbonyl group

During the reaction between carbonyl group and ammonia derivatives, a proper pH is maintained. To
increase the +ve charge of carbon for better attacking of nucleophile, a small amount of H+ (acid is
needed).

If we add excess of acid, ammonia derivatives forms its salt and thus cannot acts as a nucleophile. Thus, a
proper pH of 3.5 is needed.

All the above derivatives are crystalline solids with sharp M.P. thus, used for the identification and
characterstics of carbonyl compounds and these compounds can be decomposed with dilute mineral acids
to regenerate the original carbonyl compounds. Therefore, these derivatives are also used for the
purification of aldehydes and ketones.

2. OXIDATION REACTION

a. SIMPLE OXIDATION

Aldehydes are easily oxidised to their corresponding carboxylic acid with mild oxidising agents like
tollen’s or Fehling’s reagent while ketones cannot be oxidized by these reagents. Thus, these reactions are
useful for distinguishing among aldehydes and ketone. Upon vigorous oxidation it gives a mixture of
carboxylic acid.

By using popoff’s rule we can know thw products, according to which in unsymmeterical ketones keto
group, stays with the smaller alkyl part e.g in pentan 2 one, CH3COCH2CH2CH3 , CO group remains with
CH3 part and yields a mixture of ethanoic acid and propanoic acid not methanoic and butanoic acid.

b. TOLLEN’S TEST:-Aliphatic and aromatic Aldehydes when reacted with Tollen’s Reagent i.e.
Ammonical silver nitrate solution oxidizes to their corresponding carboxylic acid and during this silver
becomes free and deposits under test tube. Thus, this test is also known as silver mirror test.
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Ketones do not gives this test as Tollen’s Reagent is a mild oxidizing agent and ketones doesnot
undergoes mild oxidation.
AgNO3 + NH4OH AgOH + NH4NO3

AgOH + NH4OH [Ag (NH3)2] OH + 2H2O

Tollen’s reagent

Tollen’s reagent doesnot attacks on olefinic groups (double bonds) but oxidises methanoic acid to CO2
and thus, used in distinguishing methanoic and ethanoic acid.

a. FEHLING TEST:-
Fehling’s reagent is an alkaline solution of CuSO4 containing Rochelle’s salt i.e sodium potassium
tartarate.

An alkaline solution (NaOH) of rochelle’s salt called fehling B is added to an aqueous solution of CuSO4
called fehling A untill a blue ppt. of Cu(OH)2 is formed . On reacting with aliphatic Aldehydes with
Fehlings solution it get oxidized into their corresponding carboxylic Acid while Cu²⁺(cupric) reduces to
Cu⁺(cuprous) which has a brick red precipitate

CH3CHO + 2Cu2⁺ + 5OH⁻ CH3COO⁻ + Cu2O + 3H2O

(From CuSO4)(From NaOH) red ppt.

• Tartarate ions are added to prevent the precipitation of Cu²⁺ in alkaline medium by making it soluble.
• Benedict’s solution is an alkaline solution of CuSO4 with citrate ions inspite of Rochelle’s ions but it
reacts in a similar manner like that of Fehling’s reagent.
• Ketones and aromatic aledehydes do not gives this oxidation as it a mild oxidizing agent.

b. HALOFORM TEST (Iodoform test)

Ketones and aldehydes containing methyl ketone group (COCH₃) reacts with NaOH and excess of I₂ or
any halogen to form Iodoforms or other Haloforms. Among Aldehydes only Ethanal (CH₃CHO) has
(COCH₃) group So it gives a positive Idoform test.

O
NaOH
CH3 – C – H + 3I2 CCI₃– CHO CHI₃ + HCOONa
-3HI Iodoform
(yellow ppt.)
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These multiple halogenations occurred at carbon of methyl group of aldehydes, ketones and even at
alcohols always takes place in the presence of a base while the cause of this multiple halogenations is the
introduction of the first halogen which due to its electronegativity makes the remaining alpha hydrogen
more acidic and makes them easy to cleave.
It Helps us to distinguish compounds of same functional group like among ethanal and Methanal as
ethanal gives a (+ve) Idoform test while among pent -2 one or pent –3 one, pent2one has (COCH₃) group
So it gives this test positive.

3. REDUCTION REACTION

a. SIMPLE REDUCTION:-
This Reduction is mild which takes place in the presence of nickel / platinium / palladium. LiAlH4 and
NaBH4 also reduces aldehydes and ketones to their respective alcohols, though lithium aluminium hydride
is more powerful redicing agent than sodium borohydride.Both of them does not reduces isolated double
bonds.

b. REDUCTION TO PINACOLS: -

Ketones on reduction with magnesium amalgam and water forms pinacols (those alcohols having – OH
groups of adjacent carbon on same sides i.e of same spatial arrangement).
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c. CLEMMENSEN REDUCTION

The carbonyl group of aldehydes and ketones is reduced to CH2 group (alkanes) on treatment with
zinc- amalgam and concentrated hydrochloric acid.

d. WOLFF KISHNER REDUCTION

The carbonyl group of aldehydes and ketones is reduced to CH2 group (alkanes) on treatment with
hydrazine followed by heating with sodium or potassium hydroxide in high boiling solvent such as
ethylene glycol.

4. REACTIONS OF ALPHA HYDROGEN

a. ALDOL REACTION

Aldehydes and ketones having at least one α – hydrogen undergoes a condensation reaction in the
presence of base to form β – hydroxyl aldehydes (aldol , ALDehydes and OL-Alcohol) or ketol which on
further heating forms - enal products.

In all aliphatic Aldehydes and Ketones the α-Hydrogen atoms are acidic in nature. They can easily be
abstracted by a base and gives enolate ions (ene = double bond + olate = alcohol) so, NaOH is used to
make reaction more feasible. The acidity of α -H can be explained due to the presence of EWG group
(=CO) carbonyl group to it which conducts – I effect and makes its cleavage easy.

While β- hydrogen is not been acidic (as – I effect decreases with distance) so does not involves in
ALDOL as in propionaldehyde (=propanal) only α -H participates.

3 types of aldol are SELF, CROSS, INTRAMOLECULAR ALDOL.

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SELF ALDOL: - When two molecules of same aldehydes and ketones containing alpha hydrogen
condenses together in the presence of dil. Alkali i.e. NaOH (due to which its also known as BASE
CATALYSED ALDOL) to give a molecule of ALDOL, it will be referred as SELF ALDOL.

CROSS ALDOL: - When the reaction takes place between two different aldehydes and ketones or
between aldehyde and ketone, such aldol are reffered as CROSS ALDOL or MIXED ALDOL. If both of
them contains alpha hydrogen, it will yield 4 products (2 self aldol and 2 cross aldol products).

E.g ethanal and prpanal yields 4 products:

If one of the aldehyde has no alpha hydrogen, it can only serve as an acceptor, example benzaldehyde has
no alpha H but can reacts with ethanal or propanal which has alpha H.
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If a cross aldol takes place between two different or dissimilar alpha hydrogen then a maximum of 8 aldol
products are obtained. Ex. In butanone there are two types of alpha H in CH3 and in CH2 groups
CH3 – CO – CH2CH3.

INTRAMOLECULAR ALDOL VIA CYCLISATION

When a dialdehyde or a keto – aldehyde is reacted with a base, it undergoes intramolecular aldol
condensation to give ringed compounds.

b. CANNIZARO REACTION

When two moles of same aldehydes lacking alpha hydrogen reacts in the presence of a strong base
undergoes disproportionation reaction to give one mole of oxidized sodium salt of carboxylic acid and
one mole of reduced alcohol.

MECHANISM OF BENZALDEHYDE: -
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When two different aldehydes lacking alpha H are reacted in the presence of a strong base i.e NaOH then
tge reaction is known as CROSS CANNIZARO. In such reactions alcohol is obtained from less reactive
aldehyde (as its sterically hindered) while acid salt is obtained from more reactive aldehyde.

H – CHO + Ph – CHO HCOONa + PhCH2OH

In the above reaction ph – CHO (benzaldehyde; ph = phenyl) is a less reactive aldehyde due to phenyl
group and hence, forms alcohol while the more reactive methanal forms methanoic acid.

When a dialdehyde or ketoaldehyde lacking alpha H is reacted with strong base it undergoes internal
crossed cannizaro reaction.
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• CARBOXYLIC ACID

PREPERATIONS

1. FROM PRIMARY ALCOHOLS AND ALDEHYDES (OXIDATION)

• Alcohols Strong carboxylic Acid

Oxidation

e.g. - CH₃OH KMnO₄ HCOOH

• Aldehydes Mild oxidation carboxylic Acid

e.g. - CH₃CHO V₂O5 CH₃COOH

2. FROM ALKYL BENZENES

On vigorous oxidation alkylbenzenes produces Benzoic Acid, The oxidation is irrespective of carbon
chain length on Benzene as it always provides Benzoic Acid.

3. FROM THE HYDROLYSIS OF AMIDE, ACID CHLORIDES, ACYL HALIDES, NITRILES

AND ANHYDRIDES

Nitriles on complete hydrolysis produces carboxylic acid while amide on partial hydrolysis produces
Carboxylic Acid.
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PHYSICAL PROPERTIES

• Lower carboxylic Acids upto 10 are liquids while higher are waxy solids with unpleasant smell.
• Lower carboxylic acids are soluble due to the presence of extensive hydrogen bonding
(Intermolecular) it can form while by increasing carbon atom solubility decrease due to increasing
hydrocarbon (hydrophobic) part.
Intermolecular H-bonding of carboxylic acids are so strong that even they did not break at vapour phase so
carboxylic acids exists as dimer in vapour phase, moreover due to strong H–BOND , it has more M.P./B.P
and SOLUBILITY than their corresponding alcohol.

CHEMICAL PROPERTIES

• Carboxylic acids are highly acidity in nature with large value of Ka (less pKa) as after loosing H+ the
Remaining carboxylate Ion can be stabilizes through resonance
• Though it has lesser resonating structure as compare to the 5 resonating structure of phenols .But still
it’s a stronger Acid than phenol as in the resonating structure of carboxylate ion , the negative charge
is on more electronegative oxygen as compared to carbon which is less electronegative in phenoxide
ion. However, carboxylic Acids are lesser acidic than mineral Acids.
• Carboxylic acids do not give characteristic reaction of carbonyl group. This is because the lone pairs on oxygen
atom attached to hydrogen atom in the −COOH group are involved in resonance thereby making the
carbon atom less electrophilic.

1. Reaction with Metals

The reaction of carboxylic acids with metals like K, Na, Mg, and Ca results in the formation of salts. A
proton will be released from the carboxyl group of the carboxylic acid where the metal salt will occur during
the reaction phase. H2 gas is produced as a result of the reaction.
2CH3COOH+ 2Na → 2CH3COONa+ H2
2. Reaction with Alkalis
The reaction of carboxylic acids with alkalis results in the formation of salts and water.
CH3COOH+NaOH → CH3COONa+H2O
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3. Reaction with Carbonates and Bicarbonates

Carboxylic acids decompose with carbonates and bicarbonates to produce salts, vapor, and carbon dioxide
gas.
This reaction can also be used to distinguish for carboxyl groups. Carboxylic acids react with a saturated
sodium bicarbonate solution to create effervescence, which is caused by the release of CO2. With an aqueous
NaHCO3 solution, however, most phenols do not release effervescence. As a result, the reaction of
bicarbonate with carboxylic acids aids in the identification of phenols and carboxylic acids.

2CH3COOH+Na2CO3 → 2CH3COONa+ H2O+ CO2

2CH3COOH+NaHCO3 → CH3COONa +H2O + CO2

4. Formation of Acyl Chlorides

Acid chlorides are formed when carboxylic acids react with thionyl chloride (SOCl 2), phosphorus
pentachloride (PCl5), or phosphorus pentachloride (PCl5).
RCOOH+SOCl2 → RCOCl+ SO2 + HCl
RCOOH + PCl5 → RCOCl+SO2 + HCl
5. Formation of Esters (Esterification)
When carboxylic acids and alcohols are heated in the presence of concentrated sulphuric acid or dry
hydrochloric acid, fruity esters are formed.The dehydrating agent in this reaction is concentrated sulphuric
acid.
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➢ NCERT IMPORTANT LINES

• Carbonyl compounds have substantial dipole moments and are polar than ethers. The high polarity of
the carbonyl group is explained on the basis of resonance involving a neutral (A) and a dipolar (B)
structures as shown.

• Nitriles are selectively reduced by diisobutylaluminium hydride, (DIBAL-H) to imines followed by

hydrolysis to aldehydes

• Esters are also reduced to aldehydes with DIBAL-H.

• Toluene or substituted toluene is converted to benzylidene diacetate on treating with chromic oxide in
acetic anhydride. The benzylidene diacetate can be hydrolysed to corresponding benzaldehyde with
aqueous acid.

• The boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of comparable
molecular masses. It is due to weak molecular dipole-dipole interactions. Also, their boiling points are
lower than those of alcohols of similar molecular masses due to absence of intermolecular hydrogen
bonding.
• The lower members of aldehydes and ketones such as methanal, ethanal and
propanone are miscible with water in all proportions, because they form hydrogen
bond with water. However, the solubility of aldehydes and ketones decreases rapidly
on increasing the length of alkyl chain.
• A nucleophile attacks the electrophilic carbon atom of the polar carbonyl group from
a direction approximately perpendicular to the plane of sp2 hybridised orbitals of
carbonyl carbon. The hybridisation of carbon changes from sp2 to sp3 in this process,
and a tetrahedral alkoxide intermediate is produced.

• Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to steric and
electronic reasons. Sterically, the presence of two relatively large substituents in ketones hinders the
approach of nucleophile to carbonyl carbon than in aldehydes having only one such substituent.
Electronically, aldehydes are more reactive than ketones because two alkyl groups reduce the
electrophilicity of the carbonyl more effectively than in former.
JMD ੴ

• Aldehydes and ketones react with hydrogen cyanide (HCN) to yield cyanohydrins. This reaction occurs
very slowly with pure HCN. Therefore, it is catalysed by a base and the generated cyanide ion (CN-)
being a stronger nucleophile readily adds to carbonyl compounds to yield corresponding cyanohydrin.
• The hydrogensulphite addition compound of aldehydes and ketones are water soluble and can be
converted back to the original carbonyl compound by treating it with dilute mineral acid or alkali.
Therefore, these are useful for separation and purification of aldehydes.
• Dry hydrogen chloride protonates the oxygen of the carbonyl compounds and therefore, increases the
electrophilicity of the carbonyl carbon facilitating the nucleophilic attack and hence acidic medium is
used in the reactions of aldehydes and ketones with alcohols and nitrogen derivative.
• The acidity of α-hydrogen atoms of carbonyl compounds is due to the strong electron withdrawing
effect of the carbonyl group and resonance stabilisation of the conjugate base.

• Formaldehyde is well known as formalin (40%) solution used to preserve biological specimens and to
prepare bakelite. Acetaldehyde is used primarily as a starting material in the manufacture of acetic acid,
polymers and drugs. Benzaldehyde is used in perfumery and in dye industries. Acetone and ethyl methyl
ketone are common industrial solvents. Many aldehydes and ketones, e.g., butyraldehyde, vanillin,
acetophenone, camphor, etc. are well known for their odours and flavours.
• The carboxylic carbon is less electrophilic than carbonyl carbon because of the resonance.

• Aromatic carboxylic acids can be prepared by vigorous oxidation of alkyl benzenes with chromic acid
or acidic or alkaline potassium permanganate. The entire side chain is oxidised to the carboxyl group
irrespective of length of the side chain.
• Carboxylic acids are higher boiling liquids than aldehydes, ketones and even alcohols of comparable
molecular masses. This is due to more extensive intermolecular hydrogen bonding. The hydrogen bonds
are not broken completely even in the vapour phase. In fact, most carboxylic acids exist as dimer in the
vapour phase or in the aprotic solvents.
• Carboxylic acids are weaker than mineral acids, but they are stronger acids than alcohols and phenols.
The higher acidity of carboxylic acids as compared to phenols is due to. The conjugate base of
carboxylic acid, a carboxylate ion, is stabilised by two equivalent resonance structures in which the
negative charge is at the more electronegative oxygen atom. The conjugate base of phenol, a phenoxide
ion, has non-equivalent resonance structures in which the negative charge is at the less electronegative
carbon atom.
• Electron withdrawing groups increase the acidity of carboxylic acids by stabilising the conjugate base
through delocalisation of the negative charge by inductive and/or resonance effects. Conversely,
electron donating groups decrease the acidity by destabilising the conjugate base.
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• Direct attachment of groups such as phenyl or vinyl to the carboxylic acid, increases the acidity of
corresponding carboxylic acid, contrary to the decrease expected due to resonance effect it’s because of
the greater electronegativity of sp2 hybridised carbon to which carboxyl carbon is attached.
• Aromatic carboxylic acids undergo electrophilic substitution reactions in which the carboxyl group acts
as a deactivating and meta-directing group. They however, do not undergo Friedel-Crafts reaction
because the carboxyl group is deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded
to the carboxyl group.
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➢ NCERT EXEMPLAR

1. Addition of water to alkynes occurs in acidic medium and in the presence of Hg2+ ions as a catalyst.
Which of the following products will be formed on addition of water to but-1-yne under these conditions?

2. Which of the following compounds is most reactive towards nucleophilic addition reactions?

3. The correct order of increasing acidic strength is _____________.

(i) Phenol < Ethanol < Chloroacetic acid < Acetic acid
(ii) Ethanol < Phenol < Chloroacetic acid < Acetic acid
(iii) Ethanol < Phenol < Acetic acid < Chloroacetic acid
(iv) Chloroacetic acid < Acetic acid < Phenol < Ethanol

4.
(i) Phenol and benzoic acid in the presence of NaOH
(ii) Phenol and benzoyl chloride in the presence of pyridine
(iii) Phenol and benzoyl chloride in the presence of ZnCl2
(iv) Phenol and benzaldehyde in the presence of palladium
5. The reagent which does not react with both, acetone and benzaldehyde.
(i) Sodium hydrogensulphite
(ii) Phenyl hydrazine
(iii) Fehling’s solution
(iv) Grignard reagent
6. Cannizzaro’s reaction is not given by _____________.
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7.

8.

Structure of ‘A’ and type of isomerism in the above reaction are respectively.
(i) Prop–1–en–2–ol, metamerism
(ii) Prop-1-en-1-ol, tautomerism
(iii) Prop-2-en-2-ol, geometrical isomerism
(iv) Prop-1-en-2-ol, tautomerism
9. Compounds A and C in the following reaction are __________.

(i) identical
(ii) positional isomers
(iii) functional isomers
(iv) optical isomers
10. Which is the most suitable reagent for the following conversion?

(i) Tollen’s reagent

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(ii) Benzoyl peroxide

(iii) I2 and NaOH solution
(iv) Sn and NaOH solution
11. Which of the following compounds will give butanone on oxidation with alkaline KMnO4 solution?
▪ (i) Butan-1-ol
▪ (ii) Butan-2-ol
▪ (iii) Both of these
▪ (iv) None of these
12. In Clemmensen Reduction carbonyl compound is treated with _____________.
▪ (i) Zinc amalgam + HCl
▪ (ii) Sodium amalgam + HCl
▪ (iii) Zinc amalgam + nitric acid
▪ (iv) Sodium amalgam + HNO3

Multiple Choice Questions (Type-II)

Note : In the following questions two or more options may be correct.
13. Which of the following compounds do not undergo aldol condensation?

14.
▪ (i) Phenol
▪ (ii) Sodium phenoxide
▪ (iii) Sodium benzoate
▪ (iv) Benzophenone
15. Which of the following conversions can be carried out by Clemmensen Reduction?
▪ (i) Benzaldehyde into benzyl alcohol
▪ (ii) Cyclohexanone into cyclohexane
▪ (iii) Benzoyl chloride into benzaldehyde
▪ (iv) Benzophenone into diphenyl methane
16. Through which of the following reactions number of carbon atoms can be increased in the chain?
▪ (i) Grignard reaction
▪ (ii) Cannizaro’s reaction
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▪ (iii) Aldol condensation

▪ (iv) HVZ reaction
17. Benzophenone can be obtained by ____________.
▪ (i) Benzoyl chloride + Benzene + AlCl3
▪ (ii) Benzoyl chloride + Diphenyl cadmium
▪ (iii) Benzoyl chloride + Phenyl magnesium chloride
▪ (iv) Benzene + Carbon monoxide + ZnCl2

18.

Short Answer Type Questions

19. Why is there a large difference in the boiling points of butanal and butan-1-ol?
20. Write a test to differentiate between pentan-2-one and pentan-3-one.
21. Give the IUPAC names of the following compounds

22. Give the structure of the following compounds.

▪ (i) 4-Nitro Propiophenone
▪ (ii) 2-Hydroxy Cyclopentanecarbaldehyde
▪ (iii) Phenyl acetaldehyde
 JMD ੴ

23. Write IUPAC names of the following structures.

24. Benzaldehyde can be obtained from benzal chloride. Write reactions for obtaining benzal chloride and
then benzaldehyde from it.
25. Name the electrophile produced in the reaction of benzene with benzoyl chloride in the presence of
anhydrous AlCl3. Name the reaction also.
26. Oxidation of ketones involves carbon-carbon bond cleavage. Name the products formed on oxidation of 2,
5-dimethylhexane-3-one.
27. Arrange the following in decreasing order of their acidic strength and give reason for your answer.
CH3CH2OH, CH3COOH, ClCH2COOH, FCH2COOH, C6H5CH2COOH
28. What product will be formed on reaction of propanal with 2-methylpropanal in the presence of NaOH?
What products will be formed? Write the name of the reaction also.
29. Compound ‘A’ was prepared by oxidation of compound ‘B’ with alkaline KMnO 4 . Compound ‘A’
on reduction with lithium aluminium hydride gets converted back to compound ‘B’. When compound ‘A’
is heated with compound B in the presence of H2SO4 it produces fruity smell of compound C to which
family the compounds ‘A’, ‘B’ and ‘C’ belong to?
29. Arrange the following in decreasing order of their acidic strength. Give explanation for the arrangement.
C6H5COOH, FCH2COOH, NO2CH2COOH

30.
31. Carboxylic acids contain carbonyl group but do not show the nucleophilic addition reaction like
aldehydes or ketones. Why?
32. Identify the compounds A, B and C in the following reaction

33. Why are carboxylic acids more acidic than alcohols or phenols although all of them have hydrogen atom
attached to a oxygen atom (—O—H)?
34. Complete the following reaction sequence.

35. Ethylbenzene is generally prepared by acetylation of benzene followed by reduction and not by direct
alkylation. Think of a possible reason.
36. Can Gattermann-Koch reaction be considered similar to Friedel Craft’s acylation? Discuss.

Matching Type Questions

Note : Match the items of Column I and Column II in the following questions.
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38. Match the common names given in Column I with the IUPAC names given in Column II.

39. Match the acids given in Column I with their correct IUPAC names given in Column II.

40. Match the reactions given in Column I with the suitable reagents given in Column II.
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41. Match the example given in Column I with the name of the reaction in Column II.

Assertion and Reason Type Questions

Note : In the following questions a statement of assertion followed by a statement of reason is given.
Choose the correct answer out of the following choices.
(i) Assertion and reason both are correct and reason is correct explanation of assertion.
(ii) Assertion and reason both are wrong statements.
(iii) Assertion is correct statement but reason is wrong statement.
(iv) Assertion is wrong statement but reason is correct statement.
(v) Assertion and reason both are correct statements but reason is not correct explanation of assertion.

42. Assertion : Formaldehyde is a planar molecule.

Reason : It contains sp2 hybridised carbon atom.
43. Assertion : Compounds containing —CHO group are easily oxidised to corresponding carboxylic acids.
Reason : Carboxylic acids can be reduced to alcohols by treatment with LiAlH4.
44. Assertion : The α-hydrogen atom in carbonyl compounds is less acidic.
Reason : The anion formed after the loss of α-hydrogen atom is resonance stabilised.
45. Assertion : Aromatic aldehydes and formaldehyde undergo Cannizzaro reaction.
Reason : Aromatic aldehydes are almost as reactive as formaldehyde.
46. Assertion : Aldehydes and ketones, both react with Tollen’s reagent to form silver mirror.
Reason : Both, aldehydes and ketones contain a carbonyl group.

Long Answer Type Questions

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47. An alkene ‘A’ (Mol. formula C5H10) on ozonolysis gives a mixture of two compounds ‘B’ and ‘C’.
Compound ‘B’ gives positive Fehling’s test and also forms iodoform on treatment with I2 and NaOH.
Compound ‘C’ does not give Fehling’s test but forms iodoform. Identify the compounds A, B and C.
Write the reaction for ozonolysis and formation of iodoform from B and C.
48. An aromatic compound ‘A’ (Molecular formula C8H8O) gives positive 2, 4-DNP test. It gives a yellow
precipitate of compound ‘B’ on treatment with iodine and sodium hydroxide solution. Compound ‘A’
does not give Tollen’s or Fehling’s test. On drastic oxidation with potassium permanganate it forms a
carboxylic acid ‘C’ (Molecular formula C7H6O2), which is also formed along with the yellow compound
in the above reaction. Identify A, B and C and write all the reactions involved.
49. Write down functional isomers of a carbonyl compound with molecular formula C3H6O. Which isomer
will react faster with HCN and why? Explain the mechanism of the reaction also. Will the reaction lead to
the completion with the conversion of whole reactant into product at reaction conditions? If a strong acid
is added to the reaction mixture what will be the effect on concentration of the product and why?
50. When liquid ‘A’ is treated with a freshly prepared ammoniacal silver nitrate solution, it gives bright silver
mirror. The liquid forms a white crystalline solid on treatment with sodium hydrogensulphite. Liquid ‘B’
also forms a white crystalline solid with sodium hydrogensulphite but it does not give test with
ammoniacal silver nitrate. Which of the two liquids is aldehyde? Write the chemical equations of these
reactions also.

ANSWERS
I. Multiple Choice Questions (Type-I)
1. (ii) 2. (i) 3. (iii) 4. (ii) 5. (iii) 6. (iv) 7. (ii) 8. (iv) 9. (ii) 10. (iii) 11. (ii) 12. (i)
II. Multiple Choice Questions (Type-II) 13. (ii), (iv) 14. (ii), (iii) 15. (ii), (iv) 16. (i), (iii) 17.
(i), (ii) 18. (i), (ii)
III. Short Answer Type
19. Butan-1-ol has higher boiling point due to intermolecular hydrogen bonding.
20. Iodoform test
21. (i) 3-Phenylprop-2-enal (ii) Cyclohexanecarbaldehyde (iii) 3-oxopentanal (iv) But -2-enal
23. (i) Ethane-1, 2 – dial (ii) Benzene-1, 4-dicarbaldehyde (iii) 3-Bromobenzaldehyde
25. benzoyliumcation or Friedel Craft’s acylation reaction.
27. FCH2COOH > ClCH2COOH > C6H5CH2COOH > CH3COOH > CH3CH2OH
28. It is cross Aldol condensation
29. ‘A’ is a carboxylic acid, ‘B’ is an alcohol and ‘C’ is an ester.
30. NO2CH2COOH > FCH2COOH > C6H5COOH due to electron withdrawing effect.
31. Carbon atom in carbonyl compounds acquires slight positive charge and is attacked by
nucleophile.
32. Due to resonance as shown below the partial positive charge on carbonyl carbon atom is
reduced.
33. A = CH3MgBr B = CH3COOH
34. Compare the stability of anion formed after the loss of H+ ion. More stable the anion
formed, more easy will be the dissociation of O—H bond, stronger will be the acids.
IV. Matching Type
38. (i) — (d), (ii) — (e), (iii) — (a), (iv) — (b), (v) — (c) 39. (i) — (b), (ii) — (e), (iii) — (d),
(iv) — (a), (v) — (c) 40. (i) — (c), (ii) — (d), (iii) — (a), (iv) — (b) 41. (i) — (e), (ii) — (d),
(iii) — (a), (iv) — (b), (v) — (f), (vi) — (c)
V. Assertion and Reason Type
42. (i) 43. (v) 44. (iv) 45. (iii) 46. (iv)
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CHAPTER

13 ORGANIC CHEMISTRY CONTAINING NITROGEN

INTRODUCTION
• Amines constitute an important class of organic compounds derived by replacing one or more hydrogen
atoms of ammonia molecule by Alkyl or Aryl groups.
• In nature, they occur among proteins and vitamins. Biologically active compounds, Adrenaline and
ephedrine both secondary amines are used to Increase Blood pressure
• Novocain, a synthetic Amino compound is used as an anesthesia by dentist. Also Benadryl, an
Antihistamine is a 3⁰ Amine.
• Nitrogen orbitals in Amines are Sp3 Hybridized with one lone pair. Thus pyramidal ( Not perfect
tetrahedral).

PREPERATION: -

1. REDUCTION: -

2. AMMONOLYSIS OF HALOALKANES AND ALCOHOLS (HOFFMAN’S AMMONOLYSIS ;

SN2):-

Ammonia splits haloalkanes to give amine. This reaction is not much preferred as it produces a number of
by product (a contamination of 2⁰ and 3⁰ amines) as the primary amine thus obtained behaves as a
Nucleophile and can further react with alkyl halide to form 2⁰ and 3⁰ amino and finally quaternary
ammonium salt.
JMD ੴ

Though both ammonolysis of haloalkanes and alcohols are used only for preparing aliphatic amines but not
for aromatic amines as aromatic halogen (Haloarenes) and aromatic alcohols (phenols) undergoes a little
nucleophilic substitution reaction due their partial double bond character.

3. GABRIEL PTHALIMIDE SYNTHESIS OF AMINES :

Pthalimide on treatment with etanolic KOH forms potassium salts which on heating with RX followed by
alkaline hydrolysis (NaOH + H2O) produces corresponding 10 amines.

This method is preferred for preparing 1⁰ aliphatic amines as it doesn’t produce any kind as contamination
of 2⁰ and 3⁰ amines.

Also, this method is not used for preparing aromatic primary amines because haloarenes do not undergoes
nucleophilic substitution reaction (because of Sp² hybridized and partial double bond character and hence
tough to cleave).

4. HOFFMAN BROMOAMIDE DEGRADTION REACTION

This reaction is a step down (descent series) i.e. carbon decreases and produces 1⁰ amines. Amides on
reaction with Br2 or Cl2 in alkali gives 10 amines with one carbon less than its parent amides.
JMD ੴ

For example

PHYSICAL PROPERTIES

• Lower aliphatic amines are gaseous in nature with fishy smell. Upto 3 carbon are liquid and higher are
solids.
• Aniline (Aromatic amines) are usually colourless. But get coloured on storage due to atmospheric
oxidation.
• They have high M.P. and B.P. but lower than their corresponding alcohols as O–H band is more polar
than N–H bond due to the greater electronegativity of oxygen than nitrogen.
• In 1⁰ primary amines, there are two direct H atoms so it can form extensive H-bond thus it has more
M.P. /B.P. and solubility than 2⁰ and 3⁰ (3⁰ has least M.P./B.P. and solubility due to the absence of
hydrogen atom available for hydrogen bonding.)
• So, the order of M.P. /B.P. and solubility: - 1⁰ > 2⁰ > 3⁰ amines. (For isomeric amines).

CHEMICAL PROPERTIES
• Amines behave as nucleophiles due to the presence of unshared electron pair and this is also the cause
for their Basicity.
• Basicity: - R–NH₂ +H₂O R–NH₃+ +OH-

Greater the value of Kb, the stronger the Base The basic strength of amines can be expressed as pkb
So greater the value of Kb, smaller value of Pkb, more the basic will be the amines.

• Aromatic amines (Aniline) are lesser basic than aliphatic amines due to –I effect of phenyl group
• In vapour phase and non aqueous phase a 3⁰ (tertiary) amines are more basic due to the presence of 3
bulky Alkyl groups. Which are e⁻donor and conducts +I effects and increases the e⁻ density of a tertiary
amines.
So, basic order will be 3⁰>2⁰>1⁰ amines.
• In aqueous phase , except +I effect ( EDG ) , there is one more parameter hydrogen bonding that makes
any compounds stable in aqueous phase so a 2⁰ amines which has both direct hydrogen atom available
for hydrogen bonding as well as 2 alkyl groups. Which are electron donating group And conduct + I
effects is more basic than 1⁰ and 3⁰ amines.

Aliphatic amines are more basic than ammonia due to EDG (Alkyl group) while Aniline is less basic than
ammonia due to –I effect i.e the order will be aliphatic amines > ammonia > aniline.

In Aliphatic Methyl groups. 2⁰ > 1⁰ > 3⁰ (in 3⁰ maximum steric hindrance)

In Aliphatic Ethyl groups. 2⁰ > 3⁰ >1⁰ (due to more + I effect in 3⁰)

JMD ੴ

EDG increases Basicity and decreases acidity while EWG increases Acidity and Decreases the Basicity.

1. REACTION WITH CHLOROFORM (CARBYLAMINE REACTION)

Primary aliphatic and aromatic amines form Isocyanides or carbylamines with extremely unpleasant smell
on warming chloroform and alcoholic solution of KOH. So a useful test to detect 1⁰ Aliphatic / Aromatic
amine. The reaction proceeds through carbene mechanism.

C₂H5NH₂ + CHCl₃ + 3KOH warm C₂H5NC +3KCl +3H₂O

(Rotten fish smell)

2. REACTION WITH NITROUS ACID (HONO)

Nitrous acid HONO is highly unstable so prepared in this Situ from NaNO₂ + HCl at 0⁰C-5⁰C. All 3 forms
of amine (1⁰,2⁰,3⁰) with Aromatic amines reacts with HONO in different manner so very useful distinguish
among them.

Aliphatic Primary Amines forms Alcohols + N₂

Aniline (Aromatic Primary Amines ) forms Diazonium Chloride)

Secondary amines form N-Nitrosyl oils. (Yellow coloured)

Tertiary amine forms salts which have no visible trait.

JMD ੴ

3. HINSBERG TEST ( Hinsberg Regent = Benzene sulphonyl chloride )

1⁰ Amine reaction with hinsberg reagent and soluble in NaOH

2⁰ Amine reacts with Hinsberg Reagent and Insoluble in NaOH

3⁰ Amine do not reacts with Hinsberg Reagent.

REACTIONS OF AROMATIC AMINES (ANILINE)

Aniline gives substitution reactions such as Halogenation, Nitration and Suphonation. These reactions are
preceded by electophilic substitution. (Mechanism in which the attacking reagent is an electrophile as
benzene has only H+ for substitution; SE).

As aniline is a resonance hybrid so, ortho and para positions becomes highly election densed. Thus, NH2
(Amino group) acts as an ortho and para directive group (So, activates benzene towards electrophilic
substitution reactions and called as a powerful activating group)
JMD ੴ

1. HALOGENATION:

Halogenation of aniline in aqueous medium gives a trisubstituted product. For example, with Bromine
water, aniline gives a white precipitate of 2.4.6 tribromoaniline. In polar solvents like water, the
electophilicity of bromine increases, thus along with the powerful ring activation by –NH2 group It results
a trisubstituted product.

For a monosubstituted product, activity of aniline has to be decreased which can be done by acylating
aniline either by acetyl chloride (CH₃COCl) or acetic anhydride (CH₃CO)₂O in the presence of pyridine.
By doing so, the lone pair of nitrogen which increases the electron density of benzene ring indulges in
showing resonance with carbonyl group So, the reactivity decreases. This process is also called as
“MASKING”. Now, if Bromination is carried out, we have a mixture of either ortho or para products which
then reacted with dil HCl to give back aniline with a monosubstituted product. (“DEMASKING”)

2. NITRATION:-

Direct nitration of aniline yields a tarry oxidation products due to high oxidizing character of HNO3.
JMD ੴ

Due to highly acidic medium, aniline gets protonated to form anilinium ion which is a Meta directive group
So, Nitration yields a substantial amount of Meta product inspite of ortho and para directiveness of amino
group (-NH₂)

3. SULPHONATION:-

Sulphonation of aniline is somewhat different form of other ring substitution reactions. Being basic in
nature, aniline initially combines with sulphuric acid to form a salt of anilinium hydrogen sulphate which
when heated strongly forms p- amino benzene sulphonic acid also known as SULPHANILIC ACID. On
rearrangement it forms Zwitter ion (DIPOLAR ION)

NOTE: Aniline do not respond to both acylation and alkylation (FRIEDAL CRAFT REACTIONS). As the
reaction catalyst AlCl3 is a Lewis Acid and accepts a lone pair from amino group which is Lewis Base. Due
to this nitrogen acquires positive charge and hence acts as a strong deactivation group For further Reaction.
JMD ੴ

➢ NCERT IMPORTANT LINES

• Two biologically active compounds, namely adrenaline and ephedrine, both containing secondary
amino group, are used to increase blood pressure. Novocain, a synthetic amino compound, is used as an
anaesthetic in dentistry. Benadryl, a well-known antihistaminic drug also contains tertiary amino group.
• Nitro compounds are reduced to amines by passing hydrogen gas in the presence of finely divided
nickel, palladium or platinum but reduction with iron scrap and hydrochloric acid is preferred because
FeCl2 formed gets hydrolysed to release hydrochloric acid during the reaction. Thus, only a small
amount of hydrochloric acid is required to initiate the reaction.
• Ammonolysis of alcohols and haloalkanes to amines has the disadvantage of yielding a mixture of
primary, secondary and tertiary amines and also a quaternary ammonium salt. However, primary amine
is obtained as a major product by taking large excess of ammonia.
• Aromatic primary amines cannot be prepared by Gabriel pthalimide method because aryl halides do not
undergo nucleophilic substitution with the anion formed by phthalimide.
• Lower aliphatic amines are soluble in water because they can form hydrogen bonds with water
molecules. However, solubility decreases with increase in molar mass of amines due to increase in size
of the hydrophobic alkyl part. Higher amines are essentially insoluble in water.
• Alcohols are more polar than amines and form stronger intermolecular hydrogen bonds than amines and
thus possess greater boiling and solubility.
• Tertiary amines do not have intermolecular association due to the absence of hydrogen atom available
for hydrogen bond formation. Therefore, the order of boiling points of isomeric amines is as follows:
Primary > Secondary > Tertiary
• Amines have an unshared pair of electrons on nitrogen atom due to which they behave as Lewis base.
Basic character of amines can be better understood in terms of their Kb and pKb values. Larger the value
of Kb or smaller the value of pKb, stronger is the base.
• Aliphatic amines are stronger bases than ammonia due to +I effect of alkyl groups leading to high
electron density on the nitrogen atom. On the other hand, aromatic amines are weaker bases than
ammonia due to the electron withdrawing nature or resonance of the aryl group.
• The order of basicity of amines in the gaseous phase follows the expected order: tertiary amine >
secondary amine > primary amine > NH3.
• In the aqueous phase, basicity depends not only by electron releasing effect of the alkyl group (+I) but
also by solvation with water molecules and the order for methyl group is : 2O > 1 O > 3 O while for ethyl
group 2O > 3 O > 1 O
• In case of substituted aniline, it is observed that electron releasing groups like –OCH3, –CH3 increase
basic strength whereas electron withdrawing groups like –NO2, –SO3, –COOH, –X decrease it.
• Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and esters
by nucleophilic substitution reaction. This reaction is known as acylation. The products obtained by
acylation reaction are known as amides. The reaction is carried out in the presence of a base stronger
than the amine, like pyridine, which removes HCl so formed and shifts the equilibrium to the right hand
side.
JMD ੴ

• Amines also react with benzoyl chloride (C6H5COCl). This reaction is known as benzoylation.

• Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as Hinsberg’s reagent, reacts with
primary and secondary amines to form sulphonamides. The reaction of benzenesulphonyl chloride with
primary amine yields N-ethylbenzenesulphonyl amide. The hydrogen attached to nitrogen in
sulphonamide is strongly acidic due to the presence of strong electron withdrawing sulphonyl group.
Hence, it is soluble in alkali.
• Aniline reacts with bromine water at room temperature to give a white precipitate of 2,4,6
tribromoaniline. If we have to prepare monosubstituted aniline derivative it can be done by protecting
the -NH2 group by acetylation with acetic anhydride which forms acetanilide, then carrying out the
desired substitution followed by hydrolysis of the substituted amide to the substituted amine.

• The lone pair of electrons on nitrogen of acetanilide interacts with oxygen atom due to resonance Hence,
the lone pair of electrons on nitrogen is less available for donation to benzene ring by resonance.
Therefore, activating effect of –NHCOCH3 group is less than that of amino group.

• Direct nitration of aniline yields tarry oxidation products in addition to the nitro derivatives. Moreover,
in the strongly acidic medium, aniline is protonated to form the anilinium ion which is meta directing.
That is why besides the ortho and para derivatives, significant amount of meta derivative is also formed.

• However, by protecting the –NH2 group by acetylation reaction with acetic anhydride, the nitration
reaction can be controlled and the p-nitro derivative can be obtained as the major product.
JMD ੴ

• Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt formation with
aluminium chloride, the Lewis acid, which is used as a catalyst. Due to this, nitrogen of aniline acquires
positive charge and hence acts as a strong deactivating group for further reaction.
• Primary aliphatic amines form highly unstable alkyldiazonium salts Primary aromatic amines form
arenediazonium salts which are stable for a short time in solution at low temperatures (273-278 K). The
stability of arenediazonium ion is explained on the basis of resonance.
• Diazonium group being a very good leaving group, is substituted by other groups such as Cl–, Br– , I ,
CN– and OH– which displace nitrogen from the aromatic ring. The nitrogen formed escapes from the
reaction mixture as a gas.
• Certain mild reducing agents like hypophosphorous acid (phosphinic acid) or ethanol reduce diazonium
salts to arenes and they get oxidised to phosphorous acid and ethanal, respectively.

• When diazonium fluoroborate is heated with aqueous sodium nitrite solution in the presence of copper,
the diazonium group is replaced by –NO2 group.
 JMD ੴ

➢ NCERT EXEMPLAR 6. Which of the following reagents would not be a

good choice for reducing an aryl nitro compound
1. Which of the following is a 3° amine? to an amine?
▪ (i) 1-methylcyclohexylamine ▪ (i) H6(excess)/Pt
▪ (ii) Triethylamine ▪ (ii) LiAlH4in ether
▪ (iii) Fe and HCl
▪ (iii) tert-butylamine
▪ (iv) Sn and HCl
▪ (iv) N-methylaniline
7. In order to prepare a 1° amine from an alkyl
2. The correct IUPAC name for CH2 =
halide with simultaneous addition of one
CHCH2NHCH3 is
CH2 group in the carbon chain, the reagent used
▪ (i) Allylmethylamine
as source of nitrogen is ___________.
▪ (ii) 2-amino-4-pentene ▪ (i) Sodium amide, NaNH2
▪ (ii) Sodium azide, NaN3
▪ (iii) 4-aminopent-1-ene
▪ (iii) Potassium cyanide, KCN
▪ (iv) N-methylprop-2-en-1-amine
▪ (iv) Potassium phthalimide, C6H4(CO)2N–K+
3. Amongst the following, the strongest base in 8. The source of nitrogen in Gabriel synthesis of
aqueous medium is ____________. amines is _____________.
▪ (i) CH3 NH2 ▪ (i) Sodium azide, NaN3
▪ (ii) NCCH2NH2 ▪ (ii) Sodium nitrite, NaNO2
▪ (iii) (CH3)2NH ▪ (iii) Potassium cyanide, KCN
▪ (iv) C6H5NHCH3
4. Which of the following is the weakest Brönsted ▪ (iv) Potassium phthalimide, C6H4(CO)2N–K+
base? 9. Amongst the given set of reactants, the most
appropriate for preparing 2° amine is _____.
▪ (i) 2° R—Br + NH3
▪ (ii) 2° R—Br + NaCN followed by H2/Pt
▪ (iii) 1° R—NH2 + RCHO followed by H2/Pt
▪ (iv) 1° R—Br (2 mol) + potassium phthalimide
followed by H3O+/heat
10. The best reagent for converting 2-
phenylpropanamine into 2–phenylpropanamide
is _____.
▪ (i) excess H2
▪ (ii) Br2 in aqueous NaOH
▪ (iii) iodine in the presence of red phosphorus
▪ (iv) LiAlH4 in ether
11. The best reagent for converting, 2-
5. Benzylamine may be alkylated as shown in the phenylpropanamide into 1- phenylethanamine is
following equation : ____.
C6H5CH2NH2 + R—X → C6H5CH2NHR ▪ (i) excess H2/Pt
Which of the following alkylhalides is best ▪ (ii) NaOH/Br2
suited for this reaction through SN1 mechanism? ▪ (iii) NaBH4/methanol
▪ (i) CH3Br ▪ (iv) LiAlH4/ether
▪ (ii) C6H5Br 12. Hoffmann Bromamide Degradation reaction is
▪ (iii) C6H5CH2Br shown by __________.
▪ (iv) C2H5Br
▪ (i) ArNH2
▪ (ii) ArCONH2
 JMD ੴ

▪ (iii) ArNO2 18. The most reactive amine towards dilute

▪ (iv) ArCH2NH2 hydrochloric acid is ___________.
13. The correct increasing order of basic strength for
the following compounds is _________.

▪ (i) II < III < I

▪ (ii) III < I < II
▪ (iii) III < II < I
19. Acid anhydrides on reaction with primary
▪ (iv) II < I < III amines give ____________.
14. Methylamine reacts with HNO 2 to form ▪ (i) amide
_________.
▪ (ii) imide
▪ (i) CH3—O—N = O
▪ (iii) secondary amine
▪ (ii) CH3—O—CH3
▪ (iii) CH3OH ▪ (iv) imine
▪ (iv) CH3CHO
15. The gas evolved when methylamine reacts with 20.
nitrous acid is __________. ▪ (i) Sandmeyer reaction
▪ (i) NH3 ▪ (ii) Gatterman reaction
▪ (ii) N2
▪ (iii) H2 ▪ (iii) Claisen reaction
▪ (iv) C2H6 ▪ (iv) Carbylamine reaction
16. In the nitration of benzene using a mixture of
conc. H2SO4 and conc. HNO3, the species which 21. Best method for preparing primary amines from
initiates the reaction is __________. alkyl halides without changing the number of
▪ (i) NO2 carbon atoms in the chain is
▪ (ii) NO+ ▪ (i) Hoffmann Bromamide reaction
▪ (iii) NO2+
▪ (ii) Gabriel phthalimide synthesis
▪ (iv) NO2–
17. Reduction of aromatic nitro compounds using Fe ▪ (iii) Sandmeyer reaction
and HCl gives __________. ▪ (iv) Reaction with NH3
▪ (i) aromatic oxime 22. Which of the following compound will not
undergo azo coupling reaction with benzene
▪ (ii) aromatic hydrocarbon
diazonium chloride.
▪ (iii) aromatic primary amine
▪ (i) Aniline
▪ (iv) aromatic amide
▪ (ii) Phenol
▪ (iii) Anisole
▪ (iv) Nitrobenzene
 JMD ੴ

23. Which of the following compounds is the ▪ (ii) IV

weakest Brönsted base? ▪ (iii) I
▪ (iv) III
27. Which of the following methods of preparation
of amines will give same number of carbon
atoms in the chain of amines as in the reactant?
▪ (i) Reaction of nitrite with LiAlH4.
▪ (ii) Reaction of amide with LiAlH4 followed by
treatment with water.
▪ (iii) Heating alkylhalide with potassium salt of
phthalimide followed by hydrolysis.
▪ (iv) Treatment of amide with bromine in aqueous
solution of sodium hydroxide.

Multiple Choice Questions (Type-II)

Note : In the following questions two or more
24. Among the following amines, the strongest options may be correct.
Brönsted base is __________. 28. Which of the following cannot be prepared by
Sandmeyer’s reaction?
▪ (i) Chlorobenzene
▪ (ii) Bromobenzene
▪ (iii) Iodobenzene
▪ (iv) Fluorobenzene
29. Reduction of nitrobenzene by which of the
following reagent gives aniline?
▪ (i) Sn/HCl
▪ (ii) Fe/HCl
▪ (iii) H2-Pd
▪ (iv) Sn/NH4OH
30. Which of the following species are involved in
the carbylamine test?
▪ (i) R—NC
25. The correct decreasing order of basic strength of ▪ (ii) CHCl3
the following species is _______. ▪ (iii) COCl2
H2O,NH3,OH– ,NH2– ▪ (iv) NaNO2 + HCl
▪ (i) NH2– > OH– > NH3 > H2O 31. The reagents that can be used to convert
▪ (ii) OH– > NH2– > H2O > NH3 benzenediazonium chloride to benzene are
▪ (iii) NH3 > H2O > NH2– > OH– __________.
▪ (iv) H2O > NH3 > OH– > NH2–
26. Which of the following should be most volatile? ▪ (i) SnCl2 /HCl
▪ (ii) CH3CH2OH
▪ (iii) H3PO2
▪ (iv) LiAlH4
▪ (i) II
 JMD ੴ

32. The product of the following reaction is 35. Which of the following reactions are correct?
__________.

36. Under which of the following reaction

conditions, aniline gives p-nitro derivative as the
major product?
▪
33. Arenium ion involved in the bromination of ▪ (i) Acetyl chloride/pyridine followed by reaction
aniline is __________. with conc. H2SO4 + conc. HNO3.
▪ (ii) Acetic anyhdride/pyridine followed by conc.
H2SO4 + conc. HNO3.
▪ (iii) Dil. HCl followed by reaction with conc.
H2SO4 + conc. HNO3.
▪ (iv) Reaction with conc. HNO3 + conc.H2SO4 .
37. Which of the following reactions belong to
electrophilic aromatic substitution?
▪ (i) Bromination of acetanilide
▪ (ii) Coupling reaction of aryldiazonium salts
▪ (iii) Diazotisation of aniline
▪ (iv) Acylation of aniline
34. Which of the following amines can be prepared
Short Answer Type Questions
by Gabriel synthesis.
38. What is the role of HNO3 in the nitrating mixture
▪ (i) Isobutyl amine
used for nitration of benzene?
▪ (ii) 2-Phenylethylamine 39. Why is NH2 group of aniline acetylated before
▪ (iii) N-methylbenzylamine carrying out nitration?
40. What is the product when C6H5CH2NH2 reacts
▪ (iv) Aniline with HNO2?
41. What is the best reagent to convert nitrile to
primary amine?
 JMD ੴ
42. Give the structure of ‘A’ in the following
reaction.
43. What is Hinsberg reagent?
44. Why is benzene diazonium chloride not stored
and is used immediately after its preparation?
45. Why does acetylation of —NH2 group of aniline
reduce its activating effect?
46. Explain why MeNH2 is stronger base than
MeOH?
47. What is the role of pyridine in the acylation
reaction of amines?
48. Under what reaction conditions (acidic/basic),
the coupling reaction of aryldiazonium chloride
with aniline is carried out?
49. Predict the product of reaction of aniline with
bromine in non-polar solvent such as CS2.
50. Arrange the following compounds in increasing
order of dipole moment.
CH3CH2CH2, CH3CH2NH2, CH3CH2OH
51. What is the structure and IUPAC name of the
compound, allyl amine?
52.
53. A compound Z with molecular formula C3H9N
reacts with C6H5SO2Cl to give a solid, insoluble
in alkali. Identify Z.
54. A primary amine, RNH2 can be reacted with
CH3—X to get secondary amine, R—
NHCH3 but the only disadvantage is that 3°
amine and quaternary ammonium salts are also
obtained as side products. Can you suggest a
method where RNH2 forms only 2° amine?
55. Complete the following reaction.
56. Why is aniline soluble in aqueous HCl?
57. Suggest a route by which the following
conversion can be accomplished.
58. Identify A and B in the following reaction.
59. How will you carry out the following
conversions?
(i) toluene → p-toluidine
(ii) p-toluidine diazonium chloride → p-
toluic acid
60. Write following conversions:
(i) nitrobenzene → acetanilide
(ii) acetanilide → p-nitroaniline
61. A solution contains 1 g mol. each of p-toluene
diazonium chloride and p- nitrophenyl
diazonium chloride. To this 1 g mol. of alkaline
solution of phenol is added. Predict the major
product. Explain your answer.
62. How will you bring out the following
conversion?
63. How will you carry out the following
conversion?
 JMD ੴ
64. How will you carry out the following
conversion?
65. How will you carry out the following
conversions?
Matching Type Questions
Note : Match the items of Column I and Column
II in the following questions.
66. Match the reactions given in Column I with the
statements given in Column II.
67. Match the compounds given in Column I with
the items given in Column II.
Assertion and Reason Type Questions
Note : In the following questions a statement of
assertion followed by a statement of reason is
given. Choose the correct answer out of the
following choices.
(i) Both assertion and reason are wrong.
(ii) Both assertion and reason are correct
statements but reason is not correct explanation
of assertion.
(iii) Assertion is correct statement but reason is
wrong statement.
(iv) Both assertion and reason are correct
statements and reason is correct explanation of
assertion.
(v) Assertion is wrong statement but reason is
correct statement.
68. Assertion : Acylation of amines gives a
monosubstituted product whereas alkylation of
amines gives polysubstituted product.
Reason : Acyl group sterically hinders the
approach of further acyl groups.
69. Assertion : Hoffmann’s bromamide reaction is
given by primary amines.
Reason : Primary amines are more basic than
secondary amines.
70. Assertion : N-Ethylbenzene sulphonamide is
soluble in alkali.
Reason : Hydrogen attached to nitrogen in
sulphonamide is strongly acidic.
71. Assertion : N, N-Diethylbenzene sulphonamide
is insoluble in alkali.
Reason : Sulphonyl group attached to nitrogen
atom is strong electron withdrawing group.
72. Assertion : Only a small amount of HCl is
required in the reduction of nitro compounds
with iron scrap and HCl in the presence of steam.
Reason : FeCl2 formed gets hydrolysed to release
HCl during the reaction.
73. Assertion : Aromatic 1° amines can be prepared
by Gabriel Phthalimide Synthesis.
Reason : Aryl halides undergo nucleophilic
substitution with anion formed by phthalimide.
74. Assertion : Acetanilide is less basic than aniline.
Reason : Acetylation of aniline results in
decrease of electron density on nitrogen.
Long Answer Type Questions
75. A hydrocarbon ‘A’, (C4H8) on reaction with
HCl gives a compound ‘B’, (C4H9Cl), which on
reaction with 1 mol of NH3 gives compound
‘C’, (C4H11N). On reacting with NaNO2 and
HCl followed by treatment with water,
compound ‘C’ yields an optically active alcohol,
‘D’. Ozonolysis of ‘A’ gives 2 mols of
acetaldehyde. Identify compounds ‘A’ to ‘D’.
Explain the reactions involved.
76. A colourless substance ‘A’ (C6H7N) is sparingly
soluble in water and gives a water soluble
compound ‘B’ on treating with mineral acid. On
reacting with CHCl3 and alcoholic potash ‘A’
 JMD ੴ
produces an obnoxious smell due to
the formation of compound ‘C’. Reaction of ‘A’
with benzenesulphonyl chloride gives compound
‘D’ which is soluble in alkali. With NaNO2 and
HCl, ‘A’ forms compound ‘E’ which reacts with
phenol in alkaline medium to give an orange dye
‘F’. Identify compounds ‘A’ to ‘F’.
77. Predict the reagent or the product in the
following reaction sequence.
ANSWERS
I. Multiple Choice Questions (Type-I)
1. (ii) 2. (iv) 3. (iii) 4. (i) 5. (iii) 6. (ii) 7. (iii) 8.
(iv) 9. (iii) 10. (iv) 11. (ii) 12. (ii) 13. (iv) 14. (iii)
15. (ii) 16. (iii) 17. (iii) 18. (ii) 19. (i) 20. (ii) 21.
(ii) 22. (iv) 23. (iii) 24. (iv) 25. (i) 26. (ii) 27. (iii)
II. Multiple Choice Questions (Type-II)
28. (iii), (iv) 29. (i), (ii), (iii) 30. (i), (ii) 31. (ii),
(iii) 32. (i), (ii) 33. (i), (ii), (iii) 34. (i), (ii) 35. (i),
(iii) 36. (i), (ii) 37. (i), (ii)
III. Short Answer Type
38. HNO3 acts as a base in the nitrating mixture
and provides the electrophile.
40. C6H5CH2OH
41. Reduction of nitriles with sodium/alcohol or
LiAlH4 gives primary amine.
43. Benzene sulphonylchloride.
44. Benzene diazonium chloride is very unstable.
46. Nitrogen is less electronegative than oxygen
therefore lone pair of electrons on nitrogen is
readily available for donation. Hence, MeNH2 is
more basic than MeOH.
47. Pyridine and other bases are used to remove
the side product i.e. HCl from the reaction
mixture.
48. Reaction is done in mild basic conditions.
49. A mixture of 2-bromoaniline and 4-
bromoaniline is formed.
50. CH3CH2CH3 < CH3CH2NH2 < CH3CH2OH
51. CH2 == CH—CH2—NH2 , prop-2-en-1-
amine
52. N, N-Dimethylbenzenamine
53. Z is an aliphatic amine which gives a solid
insoluble in base. This implies that reaction with
C6H5SO2Cl must give a product without any
replaceable hydrogen attached to nitrogen. In
other words, the amine must be a secondary
amine. i.e. Z is ethylmethylamine.
54. Carbylamine reaction is shown by 1° amine
only which results in the replacement of two
hydrogen atoms attached to nitrogen atom of
NH2 group by one carbon atom. On catalytic
reduction the isocyanide will give a secondary
amine with one methyl group.
55. The reaction exhibits azo-coupling of
phenols. In mild alkaline conditions phenol
moiety participates in the azo-coupling and para
position of phenol is occupied.
56. Aniline forms the salt anilinium chloride
which is water soluble.
61. This reaction is an example of electrophilic
aromatic substitution. In alkaline medium,
phenol generates phenoxide ion which is more
electron rich than phenol and hence more
reactive for electrophilic attack. The electrophile
in this reaction is aryldiazonium cation. Stronger
the electrophile faster is the reaction. p-
Nitrophenyldiazonium cation is a stronger
electrophile than p-toluene diazonium cation.
Therefore, it couples preferentially with phenol.
IV. Matching Type
66. (i) → (d) (ii) → (c) (iii) → (a) (iv) → (b) 67.
(i) → (b) (ii) → (a) (iii) → (d) (iv) → (c)
V. Assertion and Reason Type
68. (iii) 69. (iii) 70. (iv) 71. (ii) 72. (iv) 73. (i)
74. (iv)
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ORGANIC NAME REACTIONS

e. Sandmeyer Reaction The Cl , Br and CN nucleophiles can easily be introduced in the benzene ring
of benzene diazonium salt in the presence of Cu(I) ion.

f. Gatterman Reaction Chlorine or bromine can be introduced in the benzene ring by treating the
benzene diazonium salt solution with corresponding halogen acid in the presence of copper powder.

g. Balz-Schiemann Reaction When BDC is treated with fluoroboric acid, benzene diazonium
fluoroborate is precipitated which on heating decomposes to yield benzenefluoride.

h. Finkelstein Reaction Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides
with NaI in dry acetone.This reaction in forward direction can be favoured by precipitating NaX
formed in dry acetone (according to Le Chatelier’s principle).

i. Swarts Reaction Heating an alkyl chloride/bromide in the presence of a metallic fluoride such as
AgF, Hg2F2, CoF2 or SbF3 gives alkyl fluorides. The reaction is termed as Swarts reaction.
Finkelstein Reaction and Swarts Reaction are known as halogen exchange reaction.

j. Wurtz Reaction Alkyl halides react with sodium in dry ether to give hydrocarbons containing double
the number of carbon atoms present in the halide. This reaction is known as Wurtz reaction.
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k. Wurtz-Fittig Reaction A mixture of an alkyl halide and aryl halide gives an alkylarene when treated
with sodium in dry ether and is called Wurtz-Fittig reaction.

l. Fittig Reaction Aryl halides also give analogous compounds when treated with sodium in dry ether,
in which two aryl groups are joined together. It is called Fittig reaction.

m. Friedel-Crafts alkylation Reaction When benzene is treated with an alkyl halide in the presence of
anhydrous aluminium chloride, alkylbenene is formed.

Note: Aromatic carboxylic acids do not undergo Friedel-Crafts reaction because the carboxyl group is
deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded to the carboxyl group.
Also, aniline does not undergo Friedal-craft reactions as being base it reacts with the reactions catalyst
aluminium chloride (Lewis acid) to form salt which deactivates the further reaction.

n. Friedel-Crafts acylation reaction The reaction of benzene with an acyl halide or acid anhydride in
the presence of Lewis acids (AlCl3) yields acyl benzene.

o. Reimer-Tiemann Reaction On treating phenol with chloroform in the presence of sodium hydroxide,
a –CHO group is introduced at ortho position of benzene ring resulting salicylaldehyde. This reaction
is known as Reimer - Tiemann reaction.
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p. Kolbe’s Reaction Phenol with sodium hydroxide gives sodium phenoxide ion which with carbon
dioxide in acidic medium results hydroxybenzoic acid (salicylic acid). This is known as Kolbe’s
reaction.

q. Rosenmund Reduction Acyl chloride (acid chloride) is hydrogenated over catalyst, palladium on
barium sulphate. To prevent the further reduction of aldehydes to primary alcohls the reaction is
carried out in the presence of xylene, quinolone or sulphur.

r. Stephen reaction Nitriles are reduced to corresponding imine with stannous chloride in the presence
of hydrochloric acid, which on hydrolysis give corresponding aldehyde. This reaction is called
Stephen reaction.

s. Etard reaction Chromyl chloride oxidizes methyl group to a chromium complex, which on
hydrolysis gives corresponding benzaldehyde.

t. Gatterman – Koch reaction When benzene or its derivative is treated with carbon monoxide and
hydrogen chloride in the presence of anhydrous aluminium chloride or cuprous chloride, it gives
benzaldehyde or substituted benzaldehyde.

u. Clemmensen Reduction The carbonyl group of aldehydes and ketones is reduced to CH2 group on
treatment with zinc- amalgam and concentrated hydrochloric acid.
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v. Wolff Kishner Reduction The carbonyl group of aldehydes and ketones is reduced to CH2 group on
treatment with hydrazine followed by heating with sodium or potassium hydroxide in high boiling
solvent such as ethylene glycol.

w. Tollens’ test On warming an aldehyde with freshly prepared ammonical silver nitrate solution
(Tollens’ reagent), a bright silver mirror is produced due to the formation of silver metal. The
aldehydes are oxidised to corresponding carboxylate anion. The reaction occurs in alkaline medium.

x. Fehling’s test Fehling reagent comprises of two solutions, Fehling solution A and Fehling solution B.
Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline sodium potassium
tartarate (Rochelle salt). These two solutions are mixed in equal amounts before test. On heating an
aldehyde with Fehling’s reagent, a reddish brown precipitate is obtained. Aldehydes are oxidised to
corresponding carboxylate anion. Aromatic aldehydes do not respond to this test.

y. Aldol reaction Aldehydes and ketones having at least one α-hydrogen undergo a reaction in the
presence of dilute alkali as catalyst to form β-hydroxy aldehydes (aldol) or β-hydroxy ketones (ketol),
respectively. This is known as Aldol reaction. The name aldol is derived from the names of the two
functional groups, aldehyde and alcohol, present in the products.

Aldol condensation. The aldol and ketol readily lose water to give α,β-unsaturated carbonyl
compounds which are aldol condensation products and the reaction is called Aldol condensation.

Cross aldol condensation: When aldol condensation is carried out between two different aldehydes
and / or ketones, it is called cross aldol condensation. If both of them contain α-hydrogen atoms, it
gives a mixture of four products.
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z. Cannizzaro reaction: Aldehydes which do not have an α-hydrogen atom, undergo self oxidation and
reduction (disproportionation) reaction on treatment with concentrated alkali. In this reaction, one
molecule of the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid salt.

aa. Kolbe electrolysis An aqueous solution of sodium or potassium salt of a carboxylic acid on
electrolysis gives alkane containing even number of carbon atoms.It is decarboxylation reaction. The
reaction is known as Kolbe electrolysis.

bb. Hell-Volhard-Zelinsky (HVZ ) reaction. Carboxylic acids having an α-hydrogen are halogenated at
the α-position on treatment with chlorine or bromine in the presence of small amount of red
phosphorus to give α-halocarboxylic acids. The reaction is known as Hell-Volhard-Zelinsky reaction.

cc. Gabriel phthalimide synthesis Gabriel synthesis is used for the preparation of pure primary amines.
Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of phthalimide
which on heating with alkyl halide followed by alkaline hydrolysis produces the corresponding
primary amine.
Aromatic primary amines cannot be prepared by this method because aryl halides do not undergo
nucleophilic substitution with the anion formed by phthalimide

dd. Hoffmann bromamide degradation reaction An amide with bromine in an aqueous or ethanolic
solution of sodium hydroxide gives primary amines. In this degradation reaction, migration of an alkyl
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or aryl group takes place from carbonyl carbon of the amide to the nitrogen atom. The amine so
formed contains one carbon less than that present in the amide.

ee. Carbylamine reaction Aliphatic and aromatic primary amines on heating with chloroform and
ethanolic potassium hydroxide form isocyanides or carbylamines which are foul smelling substances.
This reaction is known as carbylamines reaction or isocyanide test. Secondary and tertiary amines do
not show this reaction and is used as a test for primary amines.

ff. Hinsberg’s Test Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as Hinsberg’s
reagent, reacts with primary and secondary amines to form sulphonamides.
(a) The reaction of benzenesulphonyl chloride with primary amine yields N-ethylbenzenesulphonyl
amide. The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of
strong electron withdrawing sulphonyl group. Hence, it is soluble in alkali.

(b) In the reaction with secondary amine, N,N-diethyl- benzenesulphonamide is formed. Since N, N-
diethylbenzene sulphonamide does not contain any hydrogen atom attached to nitrogen atom, it is not
acidic and hence insoluble in alkali.

(c) Tertiary amines do not react with benzenesulphonyl chloride.

Note: This test is used for the distinction of primary, secondary and tertiary amines and also for the
separation of a mixture of amines.

gg. Coupling Reactions: Benzene diazonium chloride reacts with phenol in which the phenol molecule at
its para position is coupled with the diazonium salt to form p-hydroxyazobenzene. This type of
reaction is known as coupling reaction.

Similarly the reaction of diazonium salt with aniline yields p-aminoazobenzene.

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NCERT MECHANISMS
1. Alcohols are produced by the reaction of Grignard reagents with aldehydes and ketones. The first step
of the reaction is the nucleophilic addition of Grignard reagent to the carbonyl group to form an
adduct. Hydrolysis of the adduct yields an alcohol.

2. Alkenes react with water in the presence of acid as catalyst to form alcohols.

3. Ethanol undergoes dehydration by heating it with concentrated H2SO4 at 443 K.

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4. Ethanol is dehydrated in the presence of sulphuric acid at 413 K, to give ethoxyethane.

5. The reaction of an ether with concentrated HI

Step 1: The reaction takes place with HBr or HI because these reagents are sufficiently acidic.

Step 2: Iodide is a good nucleophile. It attacks the least substituted carbon of the oxonium ion formed in
step 1 and displaces an alcohol molecule by SN2 mechanism.

6. Williamson synthesis

7. Aldehyde and ketones react with hydrogen cyanide (HCN) to yield cyanohydrins.
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8. Mechanism of esterification of carboxylic acids

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ORGANIC DISTINGUISH TESTS

1. Silver nitrate test it is used to distinguish aliphatic halides and aromatic halides as aliphatic
halides gives white precipitate of silver chloride.
This test is also so use to distinguish between aliphatic halide and vinyl halides as vinyl halides do
not undergo nucleophilic substitution reaction easily so, no white precipitate will be observed in
vinyl halides.

2. Lucas test it is used to distinguish between primary, secondary and tertiary alcohols as tertiary
alcohols gives immediate turbidity with hydrochloric acid while secondary alcohol gives white
turbidity within 5 minutes and primary alcohol gives no turbidity at room temperature while gives
turbidity upon heating. In secondary and primary alcohols anhydrous zinc chloride is needed to
facilitate the reaction.

3. Phenol test in this reaction phenol is reacted with bromine water to give a white precipitate of of 2
4 6 tribromophenol.

4. Carboxylic acid test it is used to distinguish carboxylic acid from other functional groups as
carboxylic acid reacts with sodium carbonate or sodium bicarbonate to give brisk effervescence of
carbon dioxide which turns limewater milky.

5. Tollens test it is used to distinguish between aldehydes and ketones as aldehydes undergoes mild
oxidation with tollens reagent that is silver ammonical silver nitrate solution to give a silver mirror
precipitate. Ketones do not undergo mild oxidation and hence do not show this reaction.
Methanoic acid is the only carboxylic acid which giver effervescence of CO2 with tollen’s reagent
and hence, this test is used to distinguish between methanoic acid and other carboxylic acid.

6. Fehling’s test Fehling reagent comprises of two solutions, Fehling solution A and Fehling
solution B. Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline
sodium potassium tartarate (Rochelle salt). These two solutions are mixed in equal amounts before
test. On heating an aldehyde with Fehling’s reagent, a reddish brown precipitate is obtained.
Aldehydes are oxidised to corresponding carboxylate anion. Aromatic aldehydes and ketones do
not respond to this test.

7. Iodoform test this reaction is useful to distinguish the methyl ketone group as in the presence of
sodium hydroxide and iodine or sodium hypohalite it oxidises to corresponding carboxylic acids
having one carbon atom less then that of carbonyl compound and yellow precipitate of iodoform is
formed.
This reaction is also useful in distinguishing ethanal from other aldehydes as ethanal is the only
aldehyde which has methyl ketone group and shows this reaction positive. All the alcohols whose
oxidation gives methyl ketone group also shows this reaction example propan-2-ol.
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8. Nitrous acid test this reaction helps in distinguishing primary aliphatic amines and primary
aromatic amines. Primary aliphatic amines gives alcohol and nitrogen gas, due to the release of
quantitative brown gas it can be distinguished while primary aromatic amines produces benzene
diazonium salts which gives orange precipitate when treated with phenol i.e. coupling reaction.

9. Carbylamine reaction Aliphatic and aromatic primary amines on heating with chloroform and
ethanolic potassium hydroxide form isocyanides or carbylamines which are foul smelling
substances. This reaction is known as carbylamines reaction or isocyanide test. Secondary and
tertiary amines do not show this reaction and is used as a test for primary amines.
CHCl3 and CCl4 can be distinguished by this reaction as CHCl3 on reacting with R-NH2 in the
presence of a base gives isosyanide.

10. Hinsberg’s Test Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as Hinsberg’s
reagent, reacts with primary and secondary amines to form sulphonamides.

(a) The reaction of benzenesulphonyl chloride with primary amine yields N-

ethylbenzenesulphonyl amide. The hydrogen attached to nitrogen in sulphonamide is strongly
acidic due to the presence of strong electron withdrawing sulphonyl group. Hence, it is soluble in
alkali.
(b) In the reaction with secondary amine, N,N-diethyl- benzenesulphonamide is formed. Since N,
N-diethylbenzene sulphonamide does not contain any hydrogen atom attached to nitrogen atom, it
is not acidic and hence insoluble in alkali.
(c) Tertiary amines do not react with benzenesulphonyl chloride.
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ORGANIC CONVERSION TIPS

ALIPHATIC CONVERSIONS:

• Step-up conversions
(i) By Wurtz reaction
(ii) Through Potassium cyanide
(iii) Through Grignard reagent
(iv) Through Sodium Alkynide

• Step-down conversions
(i) Through Decarboxylation.
(ii) By Hofmann bromamide reaction:

S. Reagent Group Out Group In Remark

No
1 KMnO4 / H+ -CH2OH -COOH Strong Oxidation (20 alc→
ketone)
2 LiAlH4 -COOH -CH2OH Strong Reduction (ketone →
20 alc)
3 Cu / 573 K or CrO3 -CH2OH -CHO Dehydrogenation
4 PCl5 or SOCl2 -OH -Cl
5 Cl2 / Δ or Cl2 / UV -H -Cl Free radical substitution
6 Aq NaOH / KOH -X -OH Nucleophilic substitution
7 KCN -X -CN Step Up
8 AgCN -X -NC
9 Alcoholic KOH -HX = Dehydrohalogenation
(Sayetzeff’s)
10 Mg / dry ether Mg R-X → R-MgX
11 HBr >=< H and Br Markovnikov or anti-
12 H2 / Pd-BaSO4 -COCl -CHO Rosenmund Reduction
13 Zn-Hg / HCl >C=O -CH2- Clemmenson Reduction
14 NH3 / Δ -COOH -CONH2 -COOH + NH3 → -COONH2
15 Br2 / NaOH or NaOBr -CONH2 -NH2 Step Down ( Hoffmann)
16 HNO2 or NaNO2/HCl -NH2 -OH HONO
17 CHCl3 / alc KOH -NH2 -NC Carbyl amine
18 P2O5 -CONH2 -CN Dehydration
19 H3O+ -CN -COOH Hydrolysis
20 OH- -CN -CONH2
21 LiAlH4 -CN -CH2NH2 Reduction
22 Red P / Cl2 α-H of acid -Cl HVZ Reaction
IN BENZENE RING
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23 Fe / X2 /dark -H -X Halogenation
24 CH3Cl / AlCl3(anhyd) -H -CH3 Friedel Craft alkylation
25 CH3COCl / AlCl3(anhyd) -H -COCH3 Friedel Craft acylation
26 Conc.HNO3/con.H2SO4 -H -NO2 Nitration
27 Conc H2SO4 -H -SO3H Sulphonation
28 KMnO4 / H+ -R -COOH Oxidation
29 CrO2Cl2 / H+ -CH3 -CHO Mild oxidation(Etard
Reaction)
30 Sn / HCl or Fe/HCl -NO2 -NH2 Reduction
31 NaOH / 623K / 300 atm -Cl -OH
32 Zn dust / Δ -OH -H
33 NaNO2 / dil HCl / 273-278 -NH2 -N2+Cl- Diazo reaction
K
34 CuCl / HCl or Cu/HCl -N2+Cl- -Cl Sandmeyer or Gattermann
35 CuBr / HBr or Cu/HBr -N2+Cl- -Br Sandmeyer or Gattermann
36 CuCN / KCN -N2+Cl- -CN Sandmeyer
37 KI -N2+Cl- -I
38 HBF4 / Δ -N2+Cl- -F
39 H3PO2 or CH3CH2OH -N2+Cl- -H
40 H2O / 283 K -N2+Cl- -OH
41 HBF4/ NaNO2, Cu / Δ -N2+Cl- -NO2
42 C6H5-OH -N2+Cl- -N=N-C6H5-OH Coupling ( p-hydroxy)
43 C6H5-NH2 -N2+Cl- -N=N-C6H5-NH2 Coupling ( p-amino)

• Reactions of Grignard Reagent

Grignard reagent Any one below + H2O → Product

H2O or ROH or RNH2 R-H
H-CHO R-CH2-OH (10 alc)
R-CHO R-CH(OH)-R (20 alc)
R-CO-R R2C(OH)-R (30 alc)
R-MgX
CO2 R-COOH
R-CN R-CO-R
HCOOR Aldehyde
RCOOR Ketone

• Directional Properties of groups in benzene ring for electrophilic substitution

Ortho-para directing group: -R , -OH, -NH2, -X, -OR, -NHR, -NR2, -NHCOCH3, -CH2Cl, -SH, -
Ph

Meta-directing group: -NO2 , -CHO , -COOH , COOR , -CN , -SO3H , -COCH3 , -CCl3 , -NH3+ ,
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CHAPTER

12 BIOMOLECULES

Carbohydrates: Most of them have a general formula Cx (H2O)y. Earlier they were considered hydrates
of carbon. For example, glucose C6H12O6 fits into this general formula C6(H2O)6 But even acetic acid
(CH3COOH) fits into this general formula C2(H2O) and it is not a carbohydrate. Similarly, rhamnose,
C6H12O5 is a carbohydrate but does not fit into this definition.
Chemically, the carbohydrates may be defined as optically active polyhydroxy aldehydes or ketones or
the compounds which produce such units on hydrolysis.

➢ Classification:
(i) Monosaccharides: Which cannot be hydrolysed into simpler carbohydrates are called monosaccharides.
e.g., glucose (aldohexose) – C6H12O6; fructose (Ketohexose) – C6H12O6.
(ii) Oligosaccharides: Carbohydrates which upon hydrolysis yield a few (2-10) numbers of
monosaccharides are called oligosaccharides. e.g., sucrose (DISACCHARIDE), Raffinose (C18H32O16 =
Glucose+ Fructose + Galactose)
(iii) Polysaccharides: High molecular weight carbohydrates which yield more than 10 molecules of
monosaccharides on hydrolysis. e.g. starch cellulose (C6H10O5)n.
• Sugar and non-sugar: Monosaccharides and oligosaccharides are generally sweet in taste, that’s why
they are called as sugar, while polysaccharides are tasteless called non sugar.
• Reducing and non-reducing sugars: All saccharides which contain free aldehydic or ketonic group
can reduce Tollens’ reagent and Fehling’s solution are called reducing sugar otherwise non reducing
sugar.
• All monosaccharides are definitely reducing sugar. In disaccharides, maltose and lactose are reducing
sugar but sucrose is non reducing sugar.

➢ GLUCOSE:

Preparation:
(a) From Sucrose (Cane Sugar)

(b) From Starch:

• Structure of Glucose: It is an aldohexose and is also known as dextrose. Its structure (open chain) is
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➢ Evidence in favour of the above structure:

1. Its molecular formula was determined to be C6H12O6.

2. On heating (prolonged) with HI, it formed an n-hexane suggesting that all the 6 carbon atoms are in a
straight chain.

3. It reacts with hydroxylamine to form an oxime and adds a molecule of hydrogen cyanide (HCN) to
give cyanohydrin showing the presence of a carbonyl group in it

4. Glucose is oxidised to gluconic acid by mild Oxidizing agent Br. water, confirming that a carbonyl
group is an aldehyde group.

5. Acetylation with acetic anhydride gives glucose pentaacetate which confirms the presence of five –
OH groups attached to 5 different C atoms.

6. on oxidation with nitric acid, glucose well as gluconic acid both yield a dicarboxylic acid, saccharin
acid indicating the presence of -CH2OH group in it in addition to an aldehyde.

• Glucose is correctly named as D (+) glucose. ‘D’ represents the

configuration whereas (+) represents the dextro-rotatory nature of
it. The meaning of D- and L- notations is given as, all those
compounds which can be chemically correlated to (+) isomer of
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glyceraldehyde are said to have D-configuration whereas those which can be correlated to (-) isomer
of glyceraldehyde are said to have L—configuration.

➢ Cyclic structure of glucose:

1. Despite having the aldehyde group, glucose does not give 2,4-DNP test, Schiff’s test and it does not form
the hydrogensulphite addition product with NaHSO3.
2. The pentaacetate of glucose does not react with hydroxylamine indicating the absence of free —CHO
group.
3. Glucose is found to exist in two different crystalline forms which are named as α and β. The α-form of
glucose (m.p. 419 K) is obtained by crystallisation from concentrated solution of glucose at 303 K while
the β-form (m.p. 423 K) is obtained by crystallisation from hot and saturated aqueous solution at 371 K.
This behaviour could not be explained by the open chain structure for glucose.
• This behaviour could not be explained by the open-chain structure (I) for glucose. It was proposed that
one of the -OH groups may add to the -CHO group and form a cyclic hemiacetal structure. It was found
that glucose forms a six-membered ring in which -OH at C-5 is involved in a ring formation. This
explains the absence of -CHO group and also the existence of glucose in two forms as shown below.
These two cyclic forms exist in equilibrium with an open-chain structure.
• The two cyclic hemiacetal forms of glucose differ only in the configuration of the hydroxyl group at Cl,
called anomeric carbon (the aldehyde carbon before cyclization). Such isomers, i.e., a-form and b-form,
are called anomers.

• The six-membered cyclic structure of glucose is called the pyranose structure (α- or β-), in analogy
with pyran. The cyclic structure of glucose is more correctly represented by Haworth structure as
given below:

• MUTAROTATION: The spontaneous change in specific rotation of an optically active compound

with time, to an equilibrium value is called, mutarotaion. For example, the specific rotation of a freshly
prepared aqueous solution of ά-D(+) glucose falls gradually from +111 o to +52.5 o with time and that
of β-D(+) glucose increases from +19.2o to +52.5 o.
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➢ FRUCTOSE
Fructose is an important ketohexose. It is obtained along with glucose by the hydrolysis of
disaccharide, sucrose. It has a ketonic group at C – 2. It belongs to D-series and is a laevorotatory
compound. Therefore, it is written as D – (-) fructose.
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➢ NOTE:
• Sucrose: Sucrose on hydrolysis gives an equimolar mixture of D – (+) – glucose and D – (-) fructose.
Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory glucose and laevorotatory fructose.
Since the laevorotation of fructose (- 92.4°) is more than the dextrorotation of glucose (+ 52.5°), the
mixture is laevorotatory. Thus hydrolysis of sucrose brings about a change in the sign of rotation, from
Dextro (+) to leave (-) and the product is named as invert sugar.
• Lactose: It is more commonly known as milk sugar since this disaccharide is found in milk.
• Starch: Starch is the main storage polysaccharide of plants. It is a polymer of alpha-glucose and consists
of two components 15-20% of water-soluble Amylose and Amylopectin which is water-insoluble and
constitutes about 80-85% of starch.
• Cellulose: Cellulose occurs exclusively in plants. It is a predominant constituent of the cell walls of
plant cells. Cellulose is a straight-chain polysaccharide composed of only β-D-glucose units which are
joined by the glycosidic linkage
• Glycogen: The carbohydrates are stored in the animal body as glycogen. It is also known as animal
starch because its structure is similar to amylopectin and is more highly branched.
• The two monosaccharides are joined together by an oxide linkage formed by the loss of a water
molecule. Such a linkage between two monosaccharide units through oxygen atom is called glycosidic
linkage.

S. No. SACHARIDE MONOMER MONOMER BOND

1. Sucrose D-Glucose D-Fructose C1-C2
2. Maltose D-Glucose D-Glucose C1-C4
3. Lactose D-Galactose D-Glucose C1-C4
4. Cellulose D-Glucose D-Glucose C1-C4
5. Starch D-(+)-Glucose D-(+)-Glucose C1-C4

➢ PROTIENS

• Proteins are the most abundant biomolecules of the living system. Chief sources of proteins are milk,
cheese, pulses, peanuts, fish, meat, etc. They occur in every part of the body and form the fundamental
basis of structure and functions of life. They are also required for growth and maintenance of body. The
word protein is derived from Greek word, “proteios” which means primary or of prime importance. All
proteins are polymers of α-amino acids.
• Amino acids which are needed for health and growth of human beings but are not synthesized by human
body are called essential amino acids e.g., valine, leucine, phenylalanine etc.
• Amino acids which are required by us but are synthesized by the human body are called non-essential
amino acids. e. g. glycine, alanine, aspartic acid etc.
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• Amino acids are usually colourless, crystalline solids. These are

water-soluble, high melting solids and behave like salts rather than
simple amines or carboxylic acids. This behaviour is due to the
presence of both an acidic (carboxyl group) and a basic (amino
group) group in the same molecule. In an aqueous solution, the
carboxyl group can lose a proton and the amino group can accept a
proton, giving rise to a dipolar ion known as a zwitterion. This is
neutral but contains both positive and negative charges.

• In zwitterionic form, amino acids show amphoteric behaviour as they

react both with acids and bases.

• Except for glycine, all other naturally occurring a-amino acids are optically active. These exist both in
D and L forms. Most naturally occurring amino acids have L-configuration. L-Amino acids are
represented by writing the – NH2 group on the left hand.
• The isoelectric point (pI) of an amino acid is the pH at which the molecule has an average net charge
of zero and therefore does not migrate in an electric field.
• Proteins are the polymers of a-amino adds linked through peptide bond or peptide linkage.

➢ STRUCTURE OF PROTEIN:

1. PRIMARY STURCTURE: The sequence in which the various amino acids are linked to one another
in a protein molecule is called its primary structure.

2. SECONDARY STRUCTURE: Refers to the conformation which the polypeptide chains assume as a
result of H–bonding. There are two types of secondary structures.
(i) a-Helix: If the size of the groups R is large, intramolecular H-bonds are formed between C = O of one
molecule and NH of the fourth amino acid in the polypeptide chain giving right-handed a-helix structure to
the protein molecule. Examples are a-keratin in hair, nail, wool, skin etc. and myosin in muscles.
(ii) b-Flat sheet or b-pleated sheet structure: If the size of the groups R is small, intermolecular H-bonds are
formed between >C =O of one polypeptide chain with NH of the other chain giving a b-flat sheet structure
to protein molecule, i.e., silk protein fibroin.
3. TERTIARY STRUCTURE: Represents overall folding of the polypeptide chains i.e. further folding of
the secondary structure. At normal pH and temperature each protein will take up a shape (tertiary structure)
that is energetically most stable. This shape is specific to a given amino acid sequence and is called native
shape of the protein.

4. QUATERNARY STRUCTURE: The quaternary structure refers to the number of subunits and their
spatial arrangement with respect to each other in an aggregate protein molecule.
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Fibrous proteins Globular protein

1. These proteins consist of linear thread-like
molecules.
2. The polypeptide chain is extended.
3. These are insoluble in water and are
chemically inactive.
4. They serve chiefly as structural materials.
Example: Keratins, myosin.
Globular proteins are more or less spherical
molecule.
The polypeptide chain is folded, looped and
twisted.
These are soluble in water and are chemically
reactive.
They yield vital information related to the
maintenance and regulation of life processes.
Example: insulin, albumin, hemoglobin.

➢ Denaturation of Proteins: When a protein in its native form is subjected to physical change like change
in temperature or chemical change like change in pH, the hydrogen bonds are disturbed. The protein
loses its biological activity. This is called denaturing of proteins, 2° and 3° structures are destroyed, but
1° structure remains intact. The coagulation of egg white on boiling is a common example.

➢ NUCLEIC ACIDS

Nucleic acids are the polymers of nucleotides which in turn consist of a base, a pentose sugar and phosphate
moiety. Nucleic acids are responsible for the transfer of characters from parents to offsprings. There are
two types of nucleic acids — DNA and RNA. DNA contains a five-carbon sugar molecule called 2-
deoxyribose whereas RNA contains ribose. Both DNA and RNA contain adenine, guanine and cytosine.
The fourth base is thymine in DNA and uracil in RNA (thymine is 5-methyl uracil). DNA is the chemical
basis of heredity and have the coded message for proteins to be synthesized in the cell. There are three types
of RNA — mRNA, rRNA and tRNA which actually carry out the protein synthesis in the cell.

➢ CHEMICAL COMPOSITION OF NUCLEIC ACID

Complete hydrolysis of DNA (or RNA) yields a pentose sugar, phosphoric acid and nitrogen containing
heterocyclic compounds (called bases). In DNA molecules, the sugar moiety is β-D-2-deoxyribose whereas
in RNA molecule, it is β-D-ribose.

• A unit formed by the attachment of a base to the 1′ position of sugar is known as a nucleoside.
• When nucleoside is linked to phosphoric acid at 5′-position of sugar moiety we get a nucleotide
• Nucleotides are joined together by phosphodiester linkage between 5′ and 3′ carbon atoms of the pentose
sugar
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➢ FUNCTIONS OF NUCLEIC ACIDS

(i) It transfers genetic characteristics

(ii) DNA is responsible for maintaining identity of species of organisms over million of years.
(iii) DNA can replicate itself therefore, identical DNA are transferred offspring.
(iv) Various RNA help in protein synthesis but the message for synthesis of a particular protein is given by
DNA.

➢ DNA Fingerprinting is now used:

• in forensic laboratories for the identification of criminals.
• to determine the paternity of an individual.
• to identify the dead bodies in an accident by comparing the DNAs of parents or children.
• to identify racial groups to rewrite biological evolution.

DNA
1. DNA contains deoxyribose as sugar.
2. It contains thymine along with other bases-
adenine, cytosine and guanine.
3. It sends information and instruction to the cell
for manufacture of protein.
4. It has unique property of self replication. It is
responsible for maintaining heredity traits from
generation to generation.
RNA
1. RNA contains ribose as sugar.
2. It contains uracil along with other bases-
adenine, cytosine,and guanine.
3. RNA itself serves as a template for protein
synthesis.
4. It does not have property of self replication
and the genetic information passes within the
same cell from DNA to RNA then on to protein.
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VITAMINS

Vitamins are a group of organic compounds that are extremely necessary and essential for normal growth and
functioning of the human body. They are required in very small quantities but cannot be synthesized by the
body itself, and can only be sourced from outside.

Types of Vitamins

Fat Soluble Vitamins

As the name suggests these are soluble in lipids i.e. in fats. They are insoluble in water. Their absorption into
the bloodstream happens in the intestines. They are stored in human bodies as adipose tissues in the liver.
Fat-soluble types of the vitamin are not easily excreted, Hence it is very much possible to overdose on them
if they reach toxic levels in your body, This disease is hypervitaminosis. The fat-soluble vitamins are Vitamin
A, D, E and K.

Water Soluble Vitamins

These are readily dissolvable in water. Excess water-soluble vitamin in your body passes out through urine.
Since they are excreted so easily they also need to be replaced regularly. Water Soluble Vitamins are Vitamin
B and Vitamin C.
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➢ NCERT IMPORTANT LINES

• Acetic acid (CH3COOH) fits into this general formula of carbohydrtaes Cx(H2O)y, C2(H2O)2 but is not
a carbohydrate. Similarly, rhamnose, C6H12O5 is a carbohydrate but does not fit in this definition.
• Commercially glucose is obtained by hydrolysis of starch by boiling it with dilute H2SO4 at 393 K
under pressure.
• Glucose is an aldohexose and is also known as dextrose.
• Glucose is correctly named as D(+)-glucose. ‘D’ before the name of glucose represents the configuration
whereas ‘(+)’ represents dextrorotatory nature of the molecule.
• The letters ‘D’ or ‘L’ before the name of any compound indicate the relative configuration of a particular
stereoisomer of glyceraldehyde.
• Despite having the aldehyde group, glucose does not give 2,4-DNP test, Schiff’s test and it does not
form the hydrogensulphite addition product with NaHSO3. The pentaacetate of glucose does not react
with hydroxylamine all these indicating the absence of free —CHO group.
• Glucose is found to exist in two different crystalline forms which are named as α and β. The α-form of
glucose (m.p. 419 K) is obtained by crystallisation from concentrated solution of glucose at 303 K while
the β-form (m.p. 423 K) is obtained by crystallisation from hot and saturated aqueous solution at 371
K.
• This behaviour could not be explained by the open chain structure for glucose. It was proposed that one
of the —OH groups may add to the —CHO group and form a cyclic hemiacetal structure. It was found
that glucose forms a six-membered ring in which —OH at C-5 is involved in ring formation. This
explains the absence of —CHO group and also existence of glucose in two forms. These two cyclic
forms exist in equilibrium with open chain structure.
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• The two cyclic hemiacetal forms of glucose differ only in the configuration of the hydroxyl group at
C1, called anomeric carbon (the aldehyde carbon before cyclisation). Such isomers are called anomers.
• The six membered cyclic structure of glucose is called pyranose structure due to resemblance with
pyran.
• The cyclic structure of glucose is more correctly represented by Haworth structure.

• Fructose belongs to D-series and is a laevorotatory compound. It is appropriately written as D-(–)-

fructose.

• It’s cyclic five membered ring is named as furanose due to the with analogy to the compound furan.

• The two monosaccharides are joined together by an oxide linkage formed by the loss of a water
molecule. Such a linkage between two monosaccharide units through oxygen atom is called
glycosidic linkage.
• In sucrose two monosaccharides are held together by a glycosidic linkage between C1 of α-glucose and
C2 of β-fructose. Since the reducing groups of glucose and fructose are involved in glycosidic bond
formation, sucrose is a non-reducing sugar.
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• Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory glucose and laevorotatory fructose.
Since the laevorotation of fructose (–92.4°) is more than dextrorotation of glucose (+ 52.5°), the mixture
is laevorotatory. Thus, hydrolysis of sucrose brings about a change in the sign of rotation, from dextro
(+) to laevo (–) and the product is named as invert sugar.
• Maltose is composed of two α-D-glucose units in which C1 of one glucose (I) is linked to C4 of another
glucose unit (II). The free aldehyde group can be produced at C1 of second glucose in solution and it
shows reducing properties so it is a reducing sugar.
• Lactose is more commonly known as milk sugar since this disaccharide is found in milk. It is composed
of β-D-galactose and β-D-glucose. The linkage is between C1 of galactose and C4 of glucose. Hence it
is also a reducing sugar.
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➢ NCERT EXEMPLAR
1. Glycogen is a branched chain polymer of α-D-
glucose units in which chain is formed by C1—
C4 glycosidic linkage whereas branching occurs
by the formation of C1-C6 glycosidic linkage.
Structure of glycogen is similar to ______.
(i) Amylose
(ii) Amylopectin
(iii) Cellulose
(iv) Glucose
2. Which of the following polymer is stored in the
liver of animals?
(i) Amylose
(ii) Cellulose
(iii) Amylopectin
(iv) Glycogen
3. Sucrose (cane sugar) is a disaccharide. One
molecule of sucrose on hydrolysis gives
_________.
(i) 2 molecules of glucose 5. Proteins are found to have two different types of
(ii) 2 molecules of glucose + 1 molecule of fructose secondary structures viz. α-helix and β-pleated
sheet structure. α-helix structure of protein is
(iii) 1 molecule of glucose + 1 molecule of fructose
stabilised by :
(iv) 2 molecules of fructose
(i) Peptide bonds
4. Which of the following pairs represents
(ii) van der Waals forces
anomers?
(iii) Hydrogen bonds
(iv) Dipole-dipole interactions
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6. In disaccharides, if the reducing groups of (i) Nucleosides

monosaccharides i.e. aldehydic or ketonic groups (ii) Nucleotides
are bonded, these are non-reducing sugars.
Which of the following disaccharide is a non- (iii) Bases
reducing sugar? (iv) Sugars
10. Which of the following statements is not true
about glucose?
(i) It is an aldohexose.
(ii) On heating with HI it forms n-hexane.
(iii) It is present in furanose form.
(iv) It does not give 2,4-DNP test.
11. Each polypeptide in a protein has amino acids
linked with each other in a specific sequence.
This sequence of amino acids is said to be
____________.
(i) primary structure of proteins.
(ii) secondary structure of proteins.
(iii) tertiary structure of proteins.
(iv) quaternary structure of proteins.
12. DNA and RNA contain four bases each. Which
of the following bases is not present in RNA?
7. Which of the following acids is a vitamin?
(i) Adenine
(i) Aspartic acid
(ii) Uracil
(ii) Ascorbic acid
(iii) Thymine
(iii) Adipic acid
(iv) Cytosine
(iv) Saccharic acid
13. Which of the following B group vitamins can be
8. Dinucleotide is obtained by joining two
stored in our body?
nucleotides together by phosphodiester linkage.
Between which carbon atoms of pentose sugars (i) Vitamin B1
of nucleotides are these linkages present? (ii) Vitamin B2
(iii) Vitamin B6
(i) 5′ and 3′
(iv) Vitamin B12
(ii) 1′ and 5′ 14. Which of the following bases is not present in
(iii) 5′ and 5′ DNA?

(iv) 3′ and 3′ (i) Adenine

9. Nucleic acids are the polymers of (ii) Thymine

______________. (iii) Cytosine
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(iv) Uracil 18. Structure of a disaccharide formed by glucose

and fructose is given below. Identify anomeric
15. Three cyclic structures of monosaccharides are
carbon atoms in monosaccharide units.
given below which of these are anomers.

(i) ‘a’ carbon of glucose and ‘a’ carbon of fructose.

(i) I and II (ii) ‘a’ carbon of glucose and ‘e’ carbon of fructose.
(ii) II and III (iii) ‘a’ carbon of glucose and ‘b’ carbon of fructose.
(iii) I and III (iv) ‘f ’ carbon of glucose and ‘f ’ carbon of fructose.
(iv) III is anomer of I and II 19. Three structures are given below in which two
glucose units are linked. Which of these linkages
16. Which of the following reactions of glucose can
be explained only by its cyclic structure? between glucose units are between C1 and C4
and which linkages are between C1 and C6?
(i) Glucose forms pentaacetate.
(ii) Glucose reacts with hydroxylamine to form an
oxime.
(iii) Pentaacetate of glucose does not react with
hydroxylamine.
(iv) Glucose is oxidised by nitric acid to gluconic
acid.
17. Optical rotations of some compounds along with
their structures are given below which of them
have D configuration.

(i) (A) is between C1 and C4, (B) and (C) are

between C1 and C6
(ii) (A) and (B) are between C1 and C4, (C) is
between C1 and C6
(i) I, II, III (iii) (A) and (C) are between C1 and C4, (B) is
(ii) II, III between C1 and C6

(iii) I, II (iv) (A) and (C) are between C1 and C6, (B) is
between C1 and C4
(iv) III
Multiple Choice Questions (Type-II)
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Note : In the following questions two or more

options may be correct.
20. Carbohydrates are classified on the basis of their
behaviour on hydrolysis and also as reducing or
non-reducing sugar. Sucrose is a __________. (i) α-Amino acid

(i) monosaccharide (ii) Basic amino acid

(ii) disaccharide (iii) Amino acid synthesised in body
(iii) reducing sugar (iv) β-Amino acid
(iv) non-reducing sugar 25. Which of the following monosaccharides are
present as five membered cyclic structure
21. Proteins can be classified into two types on the
(furanose structure)?
basis of their molecular shape i.e., fibrous
proteins and globular proteins. Examples of (i) Ribose
globular proteins are : (ii) Glucose
(i) Insulin (iii) Fructose
(ii) Keratin (iv) Galactose
(iii) Albumin 26. In fibrous proteins, polypeptide chains are held
(iv) Myosin together by ___________.
22. Which of the following carbohydrates are (i) van der Waals forces
branched polymer of glucose? (ii) disulphide linkage
(i) Amylose (iii) electrostatic forces of attraction
(ii) Amylopectin (iv) hydrogen bonds
(iii) Cellulose 27. Which of the following are purine bases?
(iv) Glycogen (i) Guanine
23. Amino acids are classified as acidic, basic or (ii) Adenine
neutral depending upon the relative number of
amino and carboxyl groups in their molecule. (iii) Thymine
Which of the following are acidic? (iv) Uracil
28. Which of the following terms are correct about
enzyme?
(i) Proteins
(ii) Dinucleotides
(iii) Nucleic acids
(iv) Biocatalysts

24.
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Short Answer Type Questions

29. Name the sugar present in milk. How many monosaccharide units are present in it? What are such
oligosaccharides called?
30. How do you explain the presence of all the six carbon atoms in glucose in a straight chain?
31. In nucleoside a base is attached at 1′ position of sugar moiety. Nucleotide is formed by linking of
phosphoric acid unit to the sugar unit of nucleoside. At which position of sugar unit is the phosphoric acid
linked in a nucleoside to give a nucleotide?
32. Name the linkage connecting monosaccharide units in polysaccharides.
33. Under what conditions glucose is converted to gluconic and saccharic acid?
34. Monosaccharides contain carbonyl group hence are classified, as aldose or ketose. The number of carbon
atoms present in the monosaccharide molecule are also considered for classification. In which class of
monosaccharide will you place fructose?
35. The letters ‘D’ or ‘L’ before the name of a stereoisomer of a compound indicate the correlation of
configuration of that particular stereoisomer. This refers to their relation with one of the isomers of
glyceraldehyde. Predict whether the following compound has ‘D’ or ‘L’ configuration.

36. Aldopentoses named as ribose and 2-deoxyribose are found in nucleic acids. What is their relative
configuration?
37. Which sugar is called invert sugar? Why is it called so?
38. Amino acids can be classified as α-, β-, γ-, δ- and so on depending upon the relative position of amino
group with respect to carboxyl group. Which type of amino acids form polypeptide chain in proteins?
39. α-Helix is a secondary structure of proteins formed by twisting of polypeptide chain into right handed
screw like structures. Which type of interactions are responsible for making the α-helix structure stable?
40. Some enzymes are named after the reaction, where they are used. What name is given to the class of
enzymes which catalyse the oxidation of one substrate with simultaneous reduction of another substrate.
41. During curdling of milk, what happens to sugar present in it?
42. How do you explain the presence of five —OH groups in glucose molecule?
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43. Why does compound (A) given below not form an oxime?

44. Why must vitamin C be supplied regularly in diet?

45. Sucrose is dextrorotatory but the mixture obtained after hydrolysis is laevorotatory. Explain.
46. Amino acids behave like salts rather than simple amines or carboxylic acids. Explain.
47. Structures of glycine and alanine are given below. Show the peptide linkage in glycylalanine.

48. Protein found in a biological system with a unique three-dimensional structure and biological activity is
called a native protein. When a protein in its native form, is subjected to a physical change like change in
temperature or a chemical change like, change in pH, denaturation of protein takes place. Explain the
cause.
49. Activation energy for the acid catalysed hydrolysis of sucrose is 6.22 kJ mol–1, while the activation energy
is only 2.15 kJ mol–1 when hydrolysis is catalysed by the enzyme sucrase. Explain.
50. How do you explain the presence of an aldehydic group in a glucose molecule?
51. Which moieties of nucleosides are involved in the formation of phosphodiester linkages present in
dinucleotides? What does the word diester in the name of linkage indicate? Which acid is involved in the
formation of this linkage?
52. What are glycosidic linkages? In which type of biomolecules are they present?
53. Which monosaccharide units are present in starch, cellulose and glucose and which linkages link these
units?
54. How do enzymes help a substrate to be attacked by the reagent effectively?
55. Describe the term D- and L- configuration used for amino acids with examples.
56. How will you distinguish 1° and 2° hydroxyl groups present in glucose? Explain with reactions.
57. Coagulation of egg white on boiling is an example of denaturation of protein. Explain it in terms of
structural changes.

Matching Type Questions

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Note : Match the items of Column I and Column II in the following questions. More than one option
in Column II may match with the items given in Column I.
58. Match the vitamins given in Column I with the deficiency disease they cause given in Column II.

59. Match the following enzymes given in Column I with the reactions they catalyse given

Assertion and Reason Type Questions0

Note : In the following questions a statement of assertion followed by a statement of reason is given.
Choose the correct answer out of the following choices.
(i) Assertion and reason both are correct statements and reason explains the assertion.
(ii) Both assertion and reason are wrong statements.
(iii) Assertion is correct statement and reason is wrong statement.
(iv) Assertion is wrong statement and reason is correct statement.
(v) Assertion and reason both are correct statements but reason does not explain assertion.

60. Assertion : D (+) – Glucose is dextrorotatory in nature.

Reason : ‘D’ represents its dextrorotatory nature.
61. Assertion : Vitamin D can be stored in our body.
Reason : Vitamin D is fat soluble vitamin.
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62. Assertion : β-glycosidic linkage is present in maltose,

Reason : Maltose is composed of two glucose units in which C–1 of one glucose unit is linked to C–4 of
another glucose unit.
63. Assertion : All naturally occurring α-amino acids except glycine are optically active.
Reason : Most naturally occurring amino acids have L-configuration.
64. Assertion : Deoxyribose, C5H10O5 is not a carbohydrate.
Reason : Carbohydrates are hydrates of carbon so compounds which follow Cx(H2O)y formula are
carbohydrates.
65. Assertion : Glycine must be taken through diet.
Reason : It is an essential amino acid.
66. Assertion : In presence of enzyme, substrate molecule can be attacked by the reagent effectively.
Reason : Active sites of enzymes hold the substrate molecule in a suitable position

Long Answer Type Questions

67. Write the reactions of D-glucose which can’t be explained by its open-chain structure. How can cyclic
structure of glucose explain these reactions?
68. On the basis of which evidences D-glucose was assigned the following structure?

69. Carbohydrates are essential for life in both plants and animals. Name the carbohydrates that are used as
storage molecules in plants and animals, also name the carbohydrate which is present in wood or in the
fibre of cotton cloth.
70. Explain the terms primary and secondary structure of proteins. What is the difference between α-helix and
β-pleated sheet structure of proteins?
71. Write the structures of fragments produced on complete hydrolysis of DNA. How are they linked in DNA
molecule? Draw a diagram to show pairing of nucleotide bases in double helix of DNA.