Chemistry - Volume - I

INTERNATIONAL SR.SEC.
SCHOOL, NAMAKKAL
XII
CHEMISTRY
(CBSE)
2024 - 2025
VOLUME - I
.INDEX.
CHAPTE
CHAPTER NAME PAGE NO.
R
1 SOLUTIONS 01
2 CHEMICAL KINETICS 42
3 ELECTROCHEMISTRY 93
4 HALO ALKANES & HALO ARENES 139
5 ALCOHOLS, PHENOLS & ETHERS 199

SOLUTIONS
[Types of Solutions]
1 MARK QUESTIONS :
1. Give an example of a solid solution in which the solute is a gas.
Solution of hydrogen and Palladium : In this solution hydrogen which is a gas act as solute and
palladium a solid acts as a solvent
3 MARK QUESTIONS :
1. Define the term solution. How many types of solutions are formed? Write briefly about each type with
an example.
A solution is a homogeneous mixture of two or more pure substances. 1t means their composition and
properties are uniform throughout the solution. Solute and solvent are two components of a solution.
Types of solutions On the basis of different physical states of solute and solvent, solutions are of three
types mainly, which are further categorized into three.
These are listed in the following table with examples
[Expressing concentration of Solutions]

1 MARK QUESTIONS :
1. Calculate the molarity of resulting solution when 30 ml of 0.5 M H2SO4 diluted to 500 ml.
M1V1 = M2V2
30 x 0.5 = M2 x 500
M2 = 0.03M
Hreen Qark, Okl Q & A [VOLUME - I]

2
2. Define Mole fraction?

Mole Fraction : it is defined as the ratio of number of moles of one component to the total number of
moles of solute & solvent present in the solution
Mole fraction
Number of moles of the component
=
total number of moles of all components
It is denoted by x.
Take it as binary solution, the number of the moles of solute will be nB and the number of moles of
solvent will be nA, then the mole fraction of the solute in the solution is given as:
nB
xB =
nA + n B
In the same manner, the mole fraction of the solvent in the solution is given as:
nA
xA =
nA + nB
3. Define Molality?
Molality: It is the number of moles of the solute dissolved per 1000 g of the solvent. It is denoted by
‘m’
moles of solute
Molality =
mass of solvent in kg
Units for molality is moles/kg
4. Define Molarity?
Molarity: It is the number of moles of the solute dissolve per litre of the solution.
It is represented by M.
moles of solute
Molarity =
volume of solution in litres
Unit for molarity is moles/litre
5. Define Mass percentage?

Mass percentage: The mass percentage of a component in a given solution is the mass of the
component per 100 g of the solution.
Mass percentage of the component
= (mass of the component in the solution/total mass of the solution) × 100

3
2 MARK QUESTIONS :
1. Calculate the mass percentage of benzence (C6H6) and carbon tetrachloride (CCl4) if 22g of benzene
is dissolved in 122g of carbon tetrachloride.
Mass percentage of C6H6
Mass of C 6 H 6
= × 100
Total mass of the solution
Mass of C 6 H 6
= × 100
Mass of C 6 H 6 + Mass of CCl4
22
= ×100
22 + 122
= 15.28%
Mass percentage of CCl4
Mass of CCl 4
= × 100
Total mass of the solution
Mass of CCl 4
= × 100
Mass of C 6 H 6 + Mass of CCl4
122
= × 100
22 + 122
= 84. 725%
2. Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of 0.25 molal aqueous solution.
Molar mass of urea (NH2CONH2) = 2(1 × 14 + 2 ×1) + 1 × 12 + 1 × 16 = 60 g mol-1
0.25 molal aqueous solution of urea means:
1000 g of water contains 0.25 mol
= (0.25 × 60) g of urea
= 15 g of urea
i.e.,
(1000 + 15) g of solution contains 15 g of urea
Hence, 2.5 kg (2500 g) of solution contains
15 × 2500
= g
1000 + 15
= 36.95 g
= 37 g of urea (approximately)
Therefore, mass of urea required = 37 g
4
3. Concentrated nitric acid used in laboratory work is 68% nitric acid by mass in aqueous solution. What
should be the molarity of such a sample of the acid if the density of the solution is 1.504 g mL-1?
Concentrated nitric acid used in laboratory work is 68% nitric acid by mass in an aqueous solution.
This means that 68g of nitric acid is dissolved in 100 g of the solution.
Molar mass of nitric acid (HNO3)
= 1 × 1 + 1 × 14 + 3 × 16
= 63 g mol-1
Then, number of moles of HNO3
68
= mol
63
= 1.08 mol
Also density = 1.504g/mL-1 (given)
mass
Therefore from the formula, density =
Volume
100
Volume of solution = =66.49 mL
1.504
Therefore molarity of nitric acid
 1.08 
=  × 1000 = 16.24M
 66.49 
4. If the solubility product of CuS is 6 × 10-16, calculate the maximum molarity of CuS in aqueous
solution.
Solubility product of CuS, Ksp = 6 × 10-16
Let S be the solubility of CuS in mol L-1.
Now,
CuS → Cu2+ + S2-
Ksp = [Cu2+] [S2-]
= s × s = s2
Then, we have, s = K sp
s= 6 ×10−16
= 2.45 × 10-8 mol L-1.

Hence, the maximum molarity of CuS in an aqueous solution is 2.45 × 10-8 mol L-1

5
5. If the density of some lake water is 1.25 g mL-1and contains 92 g of Na+ ions per kg of water, calculate
the molality of Na+ ions in the lake.
6. Calculate the mass percentage of aspirin (C9H8O4) in acetonitrile (CH3CN) when 6.5 g of C9H8O4 is
dissolved in 450 g of CH4CN.
Mass of aspirin = 6.5 g
Mass of acrtonitrile = 450 g

Mass of solution = (6.5 + 450) g
= 456.5 g
Mass % =
( 6.5 g ) x 100
( 456.5 g )
= 1.424 %
7. Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250 mL of 0.15 M solution
in methanol.
Molarity = 0.15 M or 0.15 mol L-1
Volume solution = 250 mL = 0.25 L
Molar mass solute = (12 x 6) + (1 x 5) + (12) + (16 x 2) + (1)
= l22 g mol-1
Mass of solute = ( 0.15 x 122 x 0.25) g = 4.575 g

( Benzoic acid )

6
3 MARK QUESTIONS :
1. Calculate the mole fraction of benzene in solution containing 30% by mass in carbon tetrachloride.
Let the total mass of the solution be 100 g and the mass of benzene be 30 g.
∴ Mass of CCl4
= (100 – 30)g = 70g
Molar mass of benzene (C6H6) = (6×12 + 6 × 1) g mol-1
= 78 g mol-1
30
∴ Number of moles of C6H6 = mol
78
= 0.3846 mol
Molar mass of carbon tetrachloride (CCl4)
= 1 × 12 + 4 × 35.5
= 154 g mol-1
70
∴ Number of moles of CCl4 = mol
154
= 0.4545 mol
Thus, the mole fraction of C6H6 is given as:
Number of moles of C6 H 6
Number of moles of C6 H 6 + Number of moles of CCl4
0.3846
=
0.3846 + 0.4545
= 0.458
2. Calculate the molarity of 30 g of Co(NO3)26H2O in 4.3 L of solution

Molar mass of :
Co(NO3)26H2O = 59 + 2(14+3×16) + 6 × 18 = 291 g mol-1
30
Therefore, moles of Co(NO3)2 = mol = 0.103 mol
291
0.103mol
So, molarity = = 0.023 M
4.3L
7
3. A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution by mass. Calculate
the mass percentage of the resulting solution.
4. Nalorphene (C19H21NO3), similar to morphine, is used to combat withdrawal symptoms in narcotic
users. Dose of nalorphene generally given is L5mg Calculate the mass of 1.5 x l0-3 m aqueous
solution required for the above dose.
m = 1.5 x 10-3 m or 1.5 x 10-3 mol kg-1
Mass of solute = 1.5 x 10-3 g or 1.5 mg
Mass of solvent = ?
Molar mass of solute
(C19H21NO3) = (12 x 19) + (1 x 21) + (14) + (16 x 3)
= 311g mol-l

8
5 MARK QUESTIONS :
1. A sample of drinking water was found to be severely contaminated with chloroform (CHCl3) supposed
to a carcinogen. The level of contamination was 15 ppm (by mass) :
i) Express this in per cent by mass.
ii) Determine the molality of chloroform in the water sample.
2. Calculate (a) molality (b) molarity and (c) mole fraction of KI if the density of 20% (mass/mass)
aqueous KI is 1.202 g mL-1.
a) Molality
Weight of KI in 100 g of water = 20 g
weight of water in the solution = 100 - 20 = 80 g = 0.08 kg
Molar mass of KI = 39 + 127 = 166 g mol-1
b) Molarity
Weight of the solution = 100 g
Density of the solution = 1.202 g mL-1

9
3. A solution of glucose in water is labelled as 10% W/W. What should be the molality and mole
fraction of each component in the solution? If the density of solution is 1.2 g mL-1, then what shall be
the molarity of the solution?
Calculation of molality of the solution.

10
4. 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?
Step I : Calculating the mass ol Na2CO3 and NaHCO3
Mass of the mixture = 1.0 g
Let the mass of Na2CO3 = x g
Then the mass of NaHCO3 = (1 - x) g
According to the question, the mixture contains equimolar amounts of Na2CO3 and NaHCO3.
11
[Solubility]
1 MARK QUESTIONS :
1. How Henry’s constant (KH) varies with temperature?
Increase with increase in temperature

12
2. Define Henry’s law.

Henry’s law states that the partial pressure of the gas in the vapour phase (P) is proportional to the mole
fraction of the gas (X) in the solution.
P = KHX
Where,
P is partial pressure of gas
X is mole fraction of gas
KH is Henry’s constant
3. What is the significance of Henry’s Law constant KH?
Higher is the value of Henry’s law constant KH, lower is the solubility of the gas in the liquid.
4. Why are aquatic species more comfortable in cold water in comparison to warm water?
At a given pressure the solubility of oxygen in water increases with decrease in temperature. Presence of
more oxygen at lower temperature makes the aquatic species more comfortable in cold water.
5. Why do gases always tend to be less soluble in liquids as the temperature is raised?
Gas + Liquid ↽ ⇀ Dissolved gas; ∆H= – ve.
Dissolution of gas is an exothermic process. As the temperature is raised, the equilibrium shifts in
reverse direction (Le-Chatelier's principle). It results in decrease of solubility of gases in liquid
2 MARK QUESTIONS :
1. Write down any two applications of Henry’s law?
i) In the production of carbonated beverages to increase the solubility of CO2 gas in beverages.
ii) When scuba divers go underwater, they breathe air at high pressure. Increased pressure increases the
solubility of gases in the blood. This causes bends in scuba divers.
2. Henry’s law constant for the molarity of methane in benzene at 298 K is 4.27 ×105 mm Hg. Calculate
the solubility of methanane in benzene at 298 K under 760 mm Hg.
Here, P = 760 mm Hg
KH = 4.27 × 105 mm Hg
According to Henry’s law,
P =KH χ
P 760 mm Hg
χ= = = 177.99 × 10−5
K H 4.27 × 10 mm Hg
5
= 178 × 10-5 (approximately)

Therefore, the mole fraction of methane in benzene is 178 × 10-5

13
3. The partial pressure of ethane over a solution containing 6.56 x 10-3 g of ethane is 1 bar. If the
solution contains 5.00 x 10-2 g of ethane, then what shall be the partial pressure of gas?
According to Henry’s law
The mass of the gas (m) dissolved in solution ∝ partial pressure (p) (At constant temperature)
4. Based on solute-solvent interactions, arrange the following in order of increasing solubility in n-

octane and explain. Cyclohexane, KCl, CH3OH, CH3CN.
i) Cyclohexane and n-octane both are non-polar. So, they mix completely in a1l proportions.
ii) KCI is an ionic compound, but n-octane is non-polar. So, KCI does not dissolve in n-octane.
iii) CH3OH and CH3CN both are polar but CH3CN is less polar than CH3OH As the solvent is non-
polar, CH3CN win dissolve more than CH3OH in n-octane.
Order of solubility is KCI < CH3OH < CH3CN < cyclohexane.
5. Henry’s law constant for the methane in benzene at 298 K is 4.27 x 105 mm Hg. Calculate the
solubility of methane in benzene at 298 K under 760 mm Hg.
KH = 4.27 x 105 mm Hg (at 298 K)
P = 760 mm
Applying Henry’s law
P = KH x [x = Mole fraction/solubility of methane]
x=
P
=
( 760 mm ) = 178 x 10−5 = 1.78 x 10−3
K H ( 4.27 x 105 mm )
3 MARK QUESTIONS :
1. 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?
a) i) Deep sea divers depend upon compressed air for breathing at high pressure under water. The
compressed air contains N2 in addition to O2, which are not very soluble in blood at normal pressure.
However, at great depths when the diver breathes in compressed air from the supply tank, more N2
dissolves in the blood and other body fluids because the pressure at that depth is far greater than the

14
surface atmospheric pressure. When the diver comes towards the surface, the pressure decreases, N2
comes out of the body quickly forming bubbles in the blood stream. These bubbles restrict blood
flow, affect the transmission of nerve impulses. The bubbles can even burst the capillaries or block
them and starve the tissues of O2. This condition is called the bends, which are painful and life-
threatening.
ii) At high altitudes the partial pressure of O2 is less than that at the ground level. This results in low
concentration of oxygen in the blood and tissues of the people living at high altitudes or climbers.
The low blood oxygen causes climbers to become weak and unable to think clearly known as anoxia.
b) To increase the solubility of CO2 in soft drinks, the soda water bottles are sealed under high pressure.
When the bottle is opened at room temperature under normal atmosphere conditions, the pressure
inside the bottle decreases to atmospheric pressure and excess CO2 fizzes out.
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 0.195m, calculate Henry’s law constant.
The solubility of H2S in water at STP is 0.195m, that is, 0.195 mol of H2S is dissolved in 1000 g of
water.
1000
Moles of water = = 55.56 mol
18
∴ Mole fraction of H2S
Moles of H 2S
=
Moles of H 2S + Moles of water
0.195
=
0.195 + 55.56
= 0.0035
At STP. pressure (P) = 0.987 bar
According to Henry’s law : P = KH X
P 0.987
KH = = bar
X 0.0035
= 282 bar
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.
It is given that:
KH = 1.67 × 108 Pa
PCO 2 = 2.5atm = 2.5 ×1.01325 ×105 pa
= 2.533125 × 105 Pa

15
According to Henry’s law :P

PCO 2 = KHX
PCO 2 2.533125 × 105
x= = = 0.00152
KH 1.67 × 108
n CO2 n CO2
x= ≃
n CO2 + n H 2O n H 2O
In 500 ml of soda water, the volume of water = 500 ml [Neglect the amount of soda present]
We can write : 500ml of water = 500 g of water
500
= mol of water
18
= 27.78 mol of water
n CO2
Now, =x
n H2O
n CO2
= 0.00152
27.78
nCO2 = 0.042 mol
∴ quantity of CO2 in 500 ml of soda water
= (0.042×44)g
= 1.848 g
4. Among the following compounds, identify which are insoluble, partially soluble and highly soluble in
water?
i) Phenol ii) Toluene iii) Formic acid
iv) Ethylene glycol v) Chloroform vi) Pentanol
i) Phenol : Partially soluble (Reason : phenol has polar-OH group and non-po1ar C6H5- group).
ii) Toluene : Insoluble (Reason: Toluene is non-polar, water is polar).
iii) Formic acid : Highly soluble (Reason : Hydrogen bonding).
iv) Ethylene glycol : Highly soluble (Reason : Hydrogen bonding).
v) Chloroform : Insoluble (Reason: H-bonds are formed although polarity is present).
vi) Pentanol : Partially soluble {Reason: -OH group is polar but long hydrocarbon part is non-polar ).

16
5 MARK QUESTIONS :
1. 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. The water is in equilibrium with air at
a pressure of 10 atm. At 298 K if the Henry’s law constants for oxygen and nitrogen at 298 K are
3.30 x l07 mm and 6.51 x 107 mm respectively, calculate the composition of these gases in water.
Step I : Calculation of partial pressure of oxygen and nitrogen
( )
Partial pressure of O2 PO2 = (10 atm ) x
20
100
= 2 atm = 2 x 760 mm
Partial pressure of N2 ( PN 2 ) = (10 atm ) x

79
= 7.9 atm = 7.9 x 760 mm
100
Step II : Composition of O2 and N2 dissolved in water
The amount of gases dissolved in water is calculated in terms of their mole fractions.
[Vapour pressure of liquid solutions]

1 MARK QUESTIONS :
1. Define Ideal solution and give any two examples.
Those solutions which obey Raoult’s law over the entire range of concentration are known as ideal
solution.
∆mix H = 0
∆mix V = 0
Examples :
1. Benzene and toluene
2. n-hexane and n-heptane

17
2. Define non-ideal solutions and give any two examples.

Those solutions which do not obey Roault’s Law over the entire range of concentration are known as
non-ideal solutions.
∆mix H ≠ 0
∆mix V ≠ 0
Examples :
1. HNO3 and water
2. Acetone and CCl4
3. Explain why on addition of 1 mole of NaCl to 1L of water, the boiling point of water increases, while
addition of 1 mole of methyl alcohol to 1 L of water decreases its boiling point.
Solution. NaCl is a non-volatile solute. So, its addition to water lowers the vapour pressure of the water.
Hence, boiling point increases. Whereas methyl alcohol is more volatile than water. So, its addition to
water increases the total vapour pressure over the solution. It results in the decrease of boiling point.
2 MARK QUESTIONS :
1. Define maximum boiling point azeotropes and give one example.
Maximum boiling azeotropes are those which boil at a higher temperature than the boiling point of each
component in a pure state. They show negative deviation from Raoult’s Law.
Example :
68% HNO3 with 32% water by mass.
2. Define minimum boiling azeotropes and give one example.

Minimum boiling aeotropes are those which boil at a lower temperature than boiling point of each
component in the pure state. They show positive deviation
Example :
95.5% ethyl alcohol and 4.5% water by mass.
3. Write two differences between ideal solution and non-ideal solutions.

Ideal Solution Non-ideal solution
Obey Raoult’s law at every range of concentration. Do not obey Raoult’s law.
∆Hmix= 0; Neither heat is evolved nor absorbed ∆Hmix > 0 Endothermic
during dissolution. dissolution; heat is absorbed.

18
4. What role does the molecular interaction play in a solution of alcohol and water?
Between the molecules of alcohol as well as water, hydrogen bonding is one of the interactive forces
between the molecules. When alcohol and water are mixed together, new H-bonds also develop between
alcohol and water molecules but these are weaker than the previous ones. So, the magnitude of attractive
forces tends to decrease and the solution shows positive deviation from Raoult's law This will lead to
increase in vapour pressure of the solution and also decrease in its boiling point.
5. Suggest the most important type of intermolecular attractive 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)
i) London's forces
ii) London's forces
iii) Ion-dipole interactions
iv) Intermolecular hydrogen bonding
v) Dipole-dipole interactions
3 MARK QUESTIONS :
1. Why is it not possible to obtain pure ethanol by fractional distillation? What general name is given to
binary mixtures which show deviation from Raoult’s law and whose components cannot be separated
by fractional distillation. How many types of such mixtures are there?
The solution or mixture having same composition in liquid as well as in vapour phase and boils at a
constant temperature is known as azeotropes. Due to constant composition it cannot be separated by
fractional distillation. There are two types of azeotropes :
Minimum boiling azeotropes: Solution which shows large positive deviation from Raoult’s
law form minimum boiling azeotropes at a specific composition, e.g., ethanol-water mixture.
Maximum boiling azeotropes : Solutions which show large negative deviation from Raoult’s
law form maximum boiling azeotropes.
Example: solution having composition 68% nitric acid (HNO3) and 32% water by mass.
2. What is meant by positive and negative deviations from Raoult’s law and how is the sign of ∆mixH
related to positive and negative deviations from Raoult’s law?
According to Raoult’s law, the partial vapour pressure of each volatile component in any solution is
directly proportional to its mole fraction. The solutions which obey Raoult’s law over the entire
range of concentration are known as ideal solutions. The solutions that do not obey by Raoult’s law
are called as non-ideal solutions have vapour pressures either higher or lower than that predicted.

19
Raoult’s law (given in figure).

If the vapour pressure is higher, then the solution is said to exhibit positive deviation, and if it is
lower, then the solution is said to exhibit negative deviation form Raoult’s law.
In the case of an ideal solution, the enthalpy of the mixing of the pure components for forming the
solution is zero.
∆solH = 0
In the case of solutions showing positive deviations, absorption of heat takes place. ∆solH = Positive
In the case of solutions showing negative deviations, evolution of heat takes place. ∆solH =Negative
3. 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%
0
Let the vapour pressure of pure octane be p1 . Then, the vapour pressure of the octane after
dissolving the non – volatile solute is
80 0
p1 = 0.8p10
100
Molar mass of solute, M2 = 40 g mol-1
Mass of octane, w1 = 114 g
Molar mass of octane, (C8H18),
M1 = 8 × 12 + 18 × 1 = 114 g mol-1
Applying the relation,
p10 − p1 w 2 × M1
=
p10 M 2 × w1
p10 − 0.8 p10 w 2 ×114
=
p10 40 ×114
0.2 p10 w 2
=
p10 40
20
w2
0.2 =
40
So, w2 = 8 g
Therefore, the required mass of the solute is 8g.
4. 100 g of liquid A (molar mass 140 g mol-1) was dissolved in 1000 g of liquid B (molar mass 180 g mol-
1). The vapour pressure of pure liquid B was found to be 500 torr. Calculate the vapour pressure of
pure liquid A and its vapour pressure in the solution if the total vapour pressure of the solution is 475
torr.
100
Number of moles of liquid A, nA = mol
140
= 0.714 mol
1000
Number of moles of liquid B, nB = mol
180
= 5.556 mol
nA
Then, mole fraction of A, xA =
nA + nB
0.714
=
0.714 + 5.556
= 0.114
And, mole fraction of B, xB = 1 – 0.114 = 0.886
Now,
ptotal = pA + pB
ptotal = p0A xA + p0B xB
475 = poA × 0.114 + 500× 0.886
poA = 280.7 torr
Hence, vapour pressure of pure A = 280.7 torr
Vapour pressure of A in solution = 280.7 × 0.114
= 32 torr
5. The vapour pressure of water is 12.3 kPa at 300K. Calculate vapour pressure of 1 molal solution of a
non-volatile solute in it.
Molality of solution is 1m. It means that one mole of solute is dissolved in 1000 g of water.
Number of moles of solute (nB) = 1 mol
Number of moles of water

21
Mole fraction of solute
Mole fraction water (xA) = 1- 0.0177= 0.9823

Vapour pressure of solution
(PA) = PoA x A = (12.3 kPa) x 0.9823 = 12.08 kPa
6. Vapour pressure of water at 293K 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.
WB (solute) = 25 g; MB = 180 g mol-1; PoA = 17.535 mm
WA (water) = 450 g; MA = 18 g mol; Ps = ?
PS = 17.535 – 0.097
PS = 17.438 mm Hg
5 MARK QUESTIONS :
1. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively, at 350 K. Find out
the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find the
composition of the vapour phase.
PA0 = 450 mm of Hg
PB0 = 700 mm of Hg
Ptotal = 600 mm of Hg
Ptotal = PA0 x A + PB0 (1 − x A )
Ptotal = PA0 x A + PB0 − PB0 x A
Ptotal = ( PA0 − PB0 ) x A + PB0

22
⇒ 600 = (450 – 700)xA + 700
⇒ - 100 = -250xA
⇒ xA = 0.4
Hence, xB = 1-xA = 0.6
Now, PA = PA x A
0
= 450 × 0.4 = 180 mm of Hg
PB = PB0 x B
= 700 × 0.6
= 420 mm of Hg
PA
Now, in the vapour phase: Mole fraction A of =
PA + PB
180 180
= = = 0.30
180 + 420 600
Mole fraction of liquid B = 1-0.30
= 0.70
2. 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 heptance and 35g of octane?
Vapour pressure of heptane ( p10 ) = 105.2 kPa
Vapour pressure of octane ( p 02 ) = 46.8 kPa
We know that,
Molar mass of heptane (C7H16) = 7 × 12 + 16 × 1
= 100 g mol-1
26
∴ number of moles of heptane = mol = 0.26
100
Molar mass of octane (C8H18) = 8 × 12 + 18 ×1
= 114g mol-1

23
35
∴ Number of moles of octane mol = 0.31
114
0.26
Mole fraction of heptane, x1 =
0.26 + 0.31
= 0.456
Now, partial pressure of heptane,
p1 = x1p10
= 0.456 × 105.2
= 47.97 kPa
Partial pressure of octane,
p2 = x 2p02
= 0.544 × 46.8
= 25.46 kPa
∴vapour pressure of solution,
ptotal = pl + p2
= 47.97 + 25.46
= 73.43 kpa
3. Benzene and toluene form ideal solution over the entire range of composition. The vapour pressure of
pure benzene and toluene at 300 K are 50.71 mm Hg and 32.06 mm Hg, respectively. Calculate the
mole fraction of benzene in vapour phase if 80 g of benzene is mixed with 100 g of toluene.
Molar mass of benzene (C6H6) = 6 × 12 + 6 × 1
= 78 g mol-1
Molar mass of toluene (C6H5CH3) = 7 ×12 + 8 ×1
= 92 g mol-1
Now, number of moles present in 80 g of benzene
80
= =1.026 mol
78
Number of moles present in 100 g of toluene
100
= =1.087 mol
92

24
Therefore, Mole fraction of benzene, xb

1.026
= =0.486
1.026 + 1.087
And, mole fraction of toluene xt
xt = 1-0.486 = 0.514
Given, p0b =50.71mm Hg
p0t = 32.06mm Hg
pb = x b × p0b
Therefore, partial vapour pressure of benzene,= pb = x b × pb = 0.486 × 50.71
0
pb = 24.645mm Hg
And, partial vapour pressure of toluene, pt = x t × p0t
= 0.514 × 32.06
pt = 16.479mm Hg
Total vapour pressure = 24.65 + 16. 48
= 41.13mm H
Pb
Mole fraction of benzene in vapour phase =
Pb + Pt
24.65
= =0.60
41.13
4. A solution containing 30 g 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 2.9kPa at 298K. Calculate (i) molar mass of the solute (ii) vapour pressure of water at 298 K.
Step I : Calculation of Molar mass of the solute
Case I Number of mole of solute
Number of moles of water
Mole fraction of water

25
Vapour pressure of Ist solution (pA) = 2.8 kPa

According to Raoult's law, PA = poA xA
Vapour pressure of solution (pA) = 2.9 kPa

According to Raoult's law, pA = poA xA
According to Rauolt's law, pA = poA xA
Placing the value of M in Eq. (i)

26
[Colligative Properties and determination of Molar mass]

1 MARK QUESTIONS :
1. Among 1.0 M NaOH, 1.0 M Na2SO4, 1.0 M NH4NO3, 1.0 M KNO3 which have the highest
boiling point?
Ans: 1.0 M Na2SO4
2. What is unit of ebullioscopic constant?

Ans : K kg mol-1 or K (molality)-1
3. What is isotonic solution? Give an example.

Isotonic solutions are two solutions that have same osmotic pressure (or) concentration as a solute.
Example :
1.0M glucose solution is isotonic with 1.0M fructose solution as both solutions have the same osmotic
pressure.
0.9% NaCl Solution w.r.t Blood is isotonic solution.
4. What is hypertonic solution? Give an example.

The solution whose osmotic pressure is higher than that of other is called hypertonic solution
Example :
w
1%   NaCl Solution with Blood
v
5. What is hypotonic solution? Given an example.

A solution whose osmotic pressure is lower than that of solution from which it is separated by semi-
permeable membrane
Example :
w
0.45%   NaCl Solution with Blood
v
6. How does sprinkling of salt help in clearing the snow covered roads in hilly areas? Explain the
phenomenon involved in the process.
When salt is spread over snow covered roads it then snow will start melting from the surface because of
the depression in freezing point of water and it helps in clearing the roads.
7. Give an example of a material used for making semipermeable membrane for carrying out reverse
osmosis.
Cellulose acetate is an example of a material used for making semipermeable membrane for carrying out
reverse osmosis.

27
8. The depression in freezing point of water observed for the same amount of acetic acid, trichloroacetic
acid and trifluoroacetic acid increases in the order given above. Explain briefly.
The depression in freezing point of a solute in water depends upon on the number of particles or ions in
its aqueous solution or its degree dissociation (α). Three acids are arranged in the order of their
increasing acidic strengths as follows :
CH3COOH < CCl3COOH < CF3COOH
Fluorine is more electronegative than chlorine. So, trifluoroacetic acid is stronger than trichloroacetic
acid which in turn stronger than acetic acid. The order of depression in freezing point is also the same.
9. What is semipermeable membrane?

Continuous sheets or films (natural or synthetic) which contain a network of submicroscopic holes or
pores through which small solvent molecules (water etc.) can pass, but solute molecules of bigger size
cannot pass are called semipermeable membrane.
10. Give an example of a material used for making semi permeable membrane for carrying out reverse
osmosis.
Cellulose acetate.
11. Measurement of osmotic pressure method is preferred for the determination of molar masses of
macromolecules such as proteins and polymers.
Protein are high molecular mass material. The magnitude of colligative property depends inversely on
the molecular mass and osmotic pressure is the effective colligative peropety which depends inversely
on the molecular mass.
2 MARK QUESTIONS :
1. Calculate the freezing point of a solution containing 60 g of glucose (Molar Mass = 180 g mol-1) in
250 g of water.
(Kf of water = 1.86 K kg mol-1)
w1 = 250 g, w2 = 60 g, mw2 = 180 g / mol, Kf = 1.86 k kg mol-1
∆Tf = Kfm
w 2 ×1000 60 × 1000
∆Tf = K f × = 1.86 ×
m.w 2 × w1 (g) 180 × 250

28
1.86 × 600 1116

∆Tf = = = 2.48 K
18 × 25 450
∆Tf = T(solvent) – T(solution)
T(Solution) = T(Solvent) – ∆Tf = 273.15-2.48
= 270.67K
2. Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75 g of acetic acid to lower
its melting point by 1.5°C. Kf = 3.9 K kg mol-1.
Mass of acetic acid, M1 = 75g
Molar mass of ascorbic acid (C6H8O6),
M2 = 6 × 12 + 8 × 1 + 6 × 16
= 176 g mol-1
Lowering of melting point,
∆Tf = 1.5 K
We know that:
K f × W2 × 1000
∆Tf =
M 2 × M1
∆Tf × M 2 × M1
W2 =
K f x1000
1.5 ×176 × 75
=
3.9 ×1000
= 5.08g (approximately)
Therefore, 5.08 g of ascorbic acid is needed to be dissolved.
3. Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolving 1.0 g of
polymer of molar mass 185000 in 450 mL of water at 37o C.
Mass of polymer (WB) = 1.0 g
Molar mass of polymer [MB) = 185000 g mol-1
Volume of solution (V) =450 rnL = 0.450 L
Temperature (T) = 37 + 273 = 310 K
Solution constant (R) = 8.314 x 103 Pa L K-1 mol-1
Osmotic Pressure (π) = CRT

29
3 MARK QUESTIONS :
1. A solution of glucose (Molar mass = 180g mol-1) in water has a boiling point of 100.2°C. Calculate
the freezing point of the same solution. Molal constants for water Kf and Kb are 1.86 K kg mol-1 and
0.512 K kg mol-1 respectively.
We have given that boiling point of solution
= 100.2°C,
Kb = 0.512 K kg mol-1
Kf = 1.86 K kg mol-1
∆Tb = Tb - Tbo
= 100.2 - 100 = 0.2
∆T = Kb × molality
0.2
Therefore, molality = = 0.39
0.512
Now ∆Tf = Kf × molality
= 1.86 x 0.39
∆Tf =0.726
Therefore, the freezing point of solution, Tf = Tfo – ∆Tf
= 0 – 0.726°C
= -0.726°C
2. Boiling point of water at 750 mm Hg is 99.63° C. How much sucrose is to be added to 500 g of water
such that it boils at 100°C. Molal elevation constant for water is 0.52 K kg mol-1.
Here, elevation of boiling point,
∆Tb = (100 + 273) – (99.63 + 273)
= 0.37K
Mass of water, M1 = 500 g
Molar mass of sucrose (C12 H22 O11),
M2 = 11 ×12 + 22 × 1 + 11 × 16= 342 g mol-1
30
Molal elevation constant, Kb = 0.52 K kg mol-1

As we know that:
K × 1000 × W2
∆Tb = b
M 2 × M1
∆Tb × M 2 × M1
⇒ W2 =
K b ×1000
0.37 × 342 × 500
=
0.52 ×1000
= 121.67 g (approximately)
Therefore, 121.67g of sucrose is to be added.
3. 30 g of Urea (M = 60 g mol-1) is dissolved in 846 g of water. Calculate the vapour pressure of water
for this solution if vapour pressure of pure water at 298 K is 23.8 mm Hg.
Vapour pressure of water, P1 = 23.8 mm of Hg
Weight of water = 846 g
Weight of urea = 30 g
Molecular weight of water (H2O) = 1 × 2 + 16
= 18 g mol-1
Molecular weight or urea (NH2CONH2)
= 2N + 4H + C + O
= 2 ×14 + 4 × 1 + 12 + 16
= 60 g mol-1
846
Number of moles of water n1 = = 47
18
30
Number of mole of urea n2 = =0.5
60
Now, Let’s calculate vapour pressure of water in the solution.
We take vapour pressure as P1.
Use the formula of RLVP
 P10 − P1  n2
 =
 P1  ( n1 + n 2 )
0
putting the values we get

( 23.8 − P1 ) = 0.5
23.8 ( 47 + 0.5)

31
( 23.8 − P1 ) =0.0105
23.8
after cross multiplication
23.8-P1 = 23.8 × 0.0105
We get P1 = 23.5 mm Hg
Hence, Vapour pressure of water in the given solution = 23.5 mm of Hg
4. 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.
It is given that vapour pressure of water,
P10 = 23.8mm of Hg
Weight of water taken, W1 = 850 g
Weight of urea taken, W2 = 50 g
Molecular weight of water, M1 = 18 g mol-1
Molecular weight of urea, M2 = 60 g mol-1
Now, we have to calculate vapour pressure of water in the solution. We take vapour pressure as P1.
Now, from Raoult’s law, we get:
p10 − p1 n2
=
p10
n1 + n 2
w1 50
p − p1
0
M2 23.8 − p1 60
⇒ 0
1
= = =
p1 w w 23.8 850 50
1
+ 2 +
M1 M 2 18 60
23.8 − p1 0.83 23.8 − p1
⇒ = = 0.0173
23.8 47.22 + 0.83 23.8
p1 = 23.4 mm of Hg
Hence, the vapour pressure of water in the given solution is 23.4 mm of Hg and its relative lowering
is 0.0173.
5. 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?
Relative lowering in vapour pressure.

32
6. A 5% solution (by mass) of cane sugar in water has freezing point 271K. Calculate freezing point of
5% glucose in water if freezing point of pure water is 273.15K.
For cane sugar solution
WB (sugar) = 5 g; WA (water) = 100 - 5 = 95 g
MB (sugar) = 342 g mol-l; ∆Tf =(273.15 – 271.00)K
= 2.75 K
For glucose solution

WB (glucose) = 5 g; WA (water) = 100 - 5 = 95 g
MB (glucose) = 180 g mol-1; ∆Tf = ?
On dividing Eq. (ii) by Eq. (i)
Freezing point temperature for 5% glucose solution

= (273.15 – 4.085)K =269.07 K
7. At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure of4.98 bar. If the
osmotic pressure of the solution 1.52 bar at the same temperature, what would be its concentration?
For both solutions, R, T and V are constants.

33
For I solution
For II solution
On dividing Eq. (ii) by Eq. (i), we get
5 MARK QUESTIONS :
1. When raisin kept in water, swells in size. Name and explain the phenomenon involved with the help
of a diagram. Give three applications of the phenomenon.
Raisins swell in size on keeping in water. This happens due to the phenomenon of osmosis. The
outer skin of raisin acts as a semipermeable membrane. Water moves from a place of lower
concentration to a place of higher concentration through the semipermeable membrane. Thus, water
enters inside the raisins and make them swell.
Applications of osmosis:
Reverse osmosis is used for desalination of water. Movement of water from soil into plant
roots and subsequently into upper portion of the plant is partly due to osmosis.
Preservation of meat against bacterial action by adding salt.
Preservation of fruits against bacterial action by adding sugar. Bacterium in canned fruit loses
water through the process of osmosis, shrivels and dies.
2. Two elements A and B form compounds having formula AB2 and AB4. When dissolved in 20g of
benzene (C6H6), 1 g of AB2 lowers the freezing point by 2.3 K whereas 1.0g of AB4 lowers it by 1.3 K.
The molal depression constant for benzene is 5.1 K kg mol-1. Calculate atomic masses of A and B.

34
We know that,
1000 × w 2 × k f
M AB 2 =
∆Tf × w1
1000 ×1× 5.1
MAB2 =
2.3 × 20
Then,
MAB2 = 110.87 g mol-1
1000 ×1× 5.1

MAB4 =
1.3 × 20
= 196.15g mol-1
Now, we have the molar masses of AB2 and AB4 as 110.87g mol-1 and 196.15g mol-1, respectively.
Let the atomic masses of A and B be x and y, respectively. Now, we can write:
x + 2y = 110.87 (i)
x + 4y = 196.15 (ii)
Subtracting equation (i) from (ii), we have
2y = 85.28
⇒ y = 42.64
Putting the value of ‘y’ in equation (1), we have x + 2 × 42.64 = 110.87
⇒ x = 25.59
Hence, the atomic masses of A and B are 25.59 u and 42.64u, respectively.
3. 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?
Mass of ethylene glycol = 222.6 (Given)
Molar mass of ethylene glycol [C2H4(OH)2]
= 2 × 12 + 6 × 1 + 2 × 16
= 62
Therefore moles of ethylene glycol
= 222.6 g / 62 gmol-1
= 3.59 mol
Mass of water = 200 g

35
Therefore molality of the solution is

moles of ethylene glycol
= × 1000
mass of water
= (3.59 / 200) × 1000
= 17.95 m
Calculation of Molarity:
Moles of ethylene glycol = 3.59 mol (already calculated)
Total Mass of solution = 200 + 222. 6
= 422.6 g
mass
Volume of solution =
density volume
422.6
=
1.072
= 394.22 ml
now molarity of the solution
moles of ethylene glycol
Molarity = ×1000
volume of solution
3.59
= ×1000
394.22
Molarity = 9.11 M
[Abnormal Molar masses]

1 MARK QUESTIONS :
1. Define Abnormal molar mass:
Abnormal molar mass: When the molecular mass of a substance as determined by studying any of
the colligative properties is different than the theoretically expected value, then the substance will
have abnormal molecular mass.
2. Define Van’t Hoff factor:

Van’t Hoff factor : Van’t Hoff’s factor (i) is defined as the ratio of the observed colligative property
to the calculated colligative property.
Observed colligative property
i=
Calculated colligative property
1
Observed colligative property α
Molar Mass

36
3. Elevation of boiling point of 1 M KCl solution is nearly double than that of 1 M sugar solution.
Since the elevation of boiling point is ∆Tb = iKbm in both 1 M KCl and 1 M sugar. The solvent is
same but KCl is ionic due to which its dissociates completely. Hence the value of van’t hoff factor is
twice in 1 M KCl then 1 M sugar due to which elevation in boiling point is more.
2 MARK QUESTIONS :
1. Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water such that its osmotic pressure
is 0.75 atm at 27°C.
We know that,
n
π=i RT
V
m
π=i RT
MV
πMV
m=
iRT
π = 0.75 atm
V = 2.5L
i = 2.47
T = (27 + 273)K = 300K
Here,
R = 0.0821 L atm K-1 mol-1
M = 1 × 40 + 2 ×35.5
= 111g mol-1
0.75 ×111× 2.5
m = = 3.42 g
2.47 × 0.0821× 300
3 MARK QUESTIONS :
1. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2 L of water at
25oC, assuming that it is completely dissociated.
Amount of K2SO4 dissolved = 25 mg = 0.025 g
Volume of solution = 2 L
T = 25oC = 25 + 273 K = 298 K
Molar mass of
K2SO4 = (2 x 39) + (32) + (4 + 16) = 174 g mol-1

37
Since, K2SO4 dissociates completely as

K 2SO 4 
aq
→ 2K + + SO 24−
Total ions produced after dissociation (per mole) = 3
n ixWxRxT
So, i = 3, π = iCRT = i x RT =
V MxV
3 x ( 0.025 g ) x ( 0.0821 L atm K −1mol −1 ) x ( 298 K )

=
(174 g mol ) x ( 2L )
−1
= 5.27 x 10-3 atm
5 MARK QUESTIONS :
1. Calculate the depression in the freezing point of water when l0.g of CH3CH2CHCl COOH is added to
250 g of water. Ka = 1.4 x 10-3; Kf = 1.86 K kg mol-1.
Step I : Calculation of degree of dissociation
Mass of solute = 10 g
Molar mass of solute
(CH3CH2CHClCOOH = (12 x 4) + (1 x 7) + (35.5) + (16 x 2)
= 48 + 7 + 35.5 + 32
= 122.5 g mol-1
Molal concentration of solution
If α is the degree of dissociation of CH3CH2CHClCOOH then

CH3CH2CHClCOOH ↽ ⇀ CH3CHCICOO- + H+
Initial conc. C mol-1 kg 0 0
At equilibrium C (1 – α) Cα Cα

38
= 6.55 x 10-2 = 0.065

Step II : Calculation of van't Hoff factor (i)
CH3CH2CHClCOOH ↽ ⇀ CH3CH2CHCl COO- + H+
Initial no. of motes 1 0 0
Moles at equilibrium I-α α α
Total number of moles after dissociation
= (1- α) + (α) + (α) = (1+ α)
van't Hoff faction
= 1 + 0.065 = 1.065
Step III : Calculation of depression in freezing point (∆Tf)
∆Tf = i Kf m = (1.065) x (1.86 K kg mol-1) x (0.326 mol kg-1)
∆Tf = 0.65 K
4 MARKS QUESTIONS :
CASE STUDY QUESTIONS
1. Paragraph - 1 :
The properties of the solutions which depend only on the number of solute particles but not on the nature
of the solute are called colligative properties. Relative lowering in vapour pressure is also an example
for colligative properties.
For an experiment, sugar solution is prepared for which lowering in vapour pressure was found to be
0.061mm of Hg. (Vapour pressure of water at 20oC is 17.5mm of Hg)
Calculate the most appropriate answer for the following questions.
i) Relative lowering of vapour pressure for the given solution is
ii) The vapour pressure of solution will be

39
iii) Mole fraction of sugar in the solution is

(or)
iv) If weight of sugar taken is 5g in 108g of water then molar mass of sugar will be
Answers :
PO - PS
i) RLVP =
PO
0.061
=
17.5
= 0.00348
ii) Vapour pressure of solution,
PO - PS
From, RLVP =
PO
PS
RLVP = 1 −
PO
PS
0.00348 = 1-
17.5
PS = 17.439mm of Hg
iii) Mole fraction of solute = RLVP
= 0.00348
(or)
PO - PS n B
iv) RLVP = =
PO nA
WB M A
0.00348 = x
M B WA
5 18
0.00348 = x
M B 108
MB = 240g
2. Paragraph - 2 :
An ideal solution may be defined as the solution which obeys Raoult’s law exactly over the entire range
of concentration. The solutions for which vapour pressure is either higher or lower than that predicted
by Raoult’s law are called non-ideal solutions.
Non-ideal solutions can show either positive or negative deviations from Raoult’s law depending on
whether the A – B interactions in solutions are stronger or weaker than A – A and B – B interactions.

40
Write the most appropriate answer for the following questions.

i) Which of the following solutions is / are ideal solutions(s)?
I) Bromoethane and iodoethane
II) Acetone and chloroform
III) Benzene and acetone
IV) n-heptane and n-hexane
ii) Give an example of the solution having ∆Hmix and ∆Vmix is negative?
iii) Which of the following is not true for positive deviations?
a) The A – B interactions in solution are weaker than A – A and B – B interactions.
b) PA < PA XA and PB < PB XB
O O
c) CCl4 and CHCl3 are mixture of positive deviations.

d) All of these
(or)
iv) For water and nitric acid mixture which of the given graph is correct?
a) b)
c) Both of these d) None of these

Answers :
i) I) Bromoethane and iodoethane
IV) n-heptane and n-hexane
ii) Acetone and aniline show negative deviation, So ∆Hmix < O, ∆Vmix < O.
iii) b) PA < PA XA and PB < PB XB
O O
For positive deviations PA > PA XA and PB > PB XB

O O
(or)
iv) b) Water and nitric acid mixture shows negative deviation from Raoult’s law.

41
3. Paragraph - 3 :
Few Colligative properties are :-
a) Relative lowering of vapour pressure :
depends only on molar concentration of solute (mole fraction) and independent of its nature.
b) Depression in freezing point :
It is proportional to the molal concentration of solution.
c) Elevation of boiling point :
It is proportional to the molal concentration of solute.
d) Osmotic pressure :
It is proportional to the molar concentration of solute.
A solution of glucose is prepared with 0.052g at glucose in 80.2g of water. (Kf = 1.86K kg mol-1 and
Kb = 5.2K Kg mol–1)
Calculate the most appropriate answer for the following questions.
i) Calculate the molality of given solution?
ii) Calculate boiling point for the given solution?
iii) Calculate depression in freezing point of solution?
(or)
iv) Calculate mole fraction of glucose in given solution?
Answers :
WB 1000
i) m= x
M B WA
0.052 1000
= x
180 80.2
= 0.0036m
ii) ∆Tb = Kb x m
= 5.2 x 0.0036 = 0.0187K
Tb = 373 + 0.0187 = 373.0187K
iii) ∆Tf = Kf x m
= 1.86 x 0.0036 = 0.067K
0.052
iv) Moles of glucose = = 0.00028
180
80.2
Moles of water = = 4.455
18
0.00028
Mole fraction of glucose =
0.00028 + 4.45
= 6.28 x 10-5
42
CHEMICAL KINETICS
[Rate law of chemical reaction]
1 MARK QUESTIONS :
1. For the assumed reaction X2 + 3Y2 → 2XY3 , write the rate of equation in terms of rate of
disappearance of Y2.
d [X2 ] 1 d [ Y2 ] 1 d [ XY3 ]
Rate = − =− =+
dt 3 dt 2 dt
d [ Y2 ] d [X2 ] 3 d [ XY3 ]
Rate of disappearance of Y2 = − = −3 =+
dt dt 2 dt
2. For the reaction, 3H2(g) + N2(g) → 2NH3(g), how are the rate expressions
d [ H2 ] d [ NH3 ]
− and interrelated?
dt dt
1 d [ H2 ] 1 d [ NH3 ]
Rate of reaction = − . =
3 dt 2 dt
3. Express the rate of the following reaction in terms of disappearance of hydrogen in the reaction.
N2(g) + 3H2 (g) → 2NH3(g)
1 d [ H2 ]
− = Rate of reaction.
3 dt
4. Thermodynamic feasibility of the reaction alone cannot decide the rate of the reaction. Explain with
the help of one example.
Thermodynamically the conversion of diamond to graphite is highly feasible but this reaction is very
slow because its activation energy is high.
5. Why most people think that diamond is forever?

According to thermodynamic data indicate that diamond shall convert to graphite but in reality the
conversion rate is so slow that the change is not perceptible at all.
6. Give an example for moderate reaction.

Inversion of cane sugar, hydrolysis of starch.

43
7. What is the condition for rate of reaction is to be same as that of rate of disappearance of the reactant
and rate of appearance of product?
If stoichiometric coefficients of the reactants and products are one mole then rate of reaction is same as
the rate of disappearance of the reactant and rate of appearance of product.
A ( g ) → B( g)
∆ (A) ∆ ( B)
rate of reaction = − =+
∆t ∆t
8. Why rate can also be expressed for a gaseous reaction as rate of change in partial pressure of the
reactant or the product?
For a gaseous reaction at constant temperature, concentration is directly proportional to the partial
pressure of species.
9. What happens to the rate of reaction with the passage of time as the concentration of reactants
decrease?
rate of reaction decreases.
2 MARK QUESTIONS :
1. A chemical reaction 2A ⇌ 4B + C in gas phase occurs in a closed vessel. The concentration of B is
found to increase by 5 x 10-3 mol L-1 in 10 seconds. Calculate (i) Rate of appearance of B. (ii) Rate
of disappearance of A.
Increase in conc. of B
Rate of appearance of B =
Time int erval
5 x 10−3
=
10
= 5 x 10-4 mol L–1 s–1
2 1 d [ A ] 1 d [ B]
Rate of disappearance of A = x Rate of appearance of B, Since − =
4 2 dt 4 dt
1
= x 5 x 10−4
2
= 2.5 x 10-4 mol L-1 s-1
2. Average rate of reaction does not give the true picture of the reaction rate. Explain.
Average rate of reaction is obtained by dividing the change in concentration of a particular species by
the time interval. As the concentration changes are not uniform, the average rate does not give a true
picture of the reaction rate.
44
3. For the reaction 2N2O5(g) → 4NO2(g) + O2(g) the rate of formation of NO2(g) is 2.8 x 10-3Ms-1.
Calculate the rate of disappearance of N2O5(g).
1
= x 2.8 x 10-3 Ms-1 = 1.4 x 10-3 Ms-1
2
3 MARK QUESTIONS :
1. A + 2B → 3C + 2D. The rate of disappearance of B is 1 x 10-2 mol L-1 S-1 . What will be (i) rate of
reaction, (ii) rate change in concentration of A and C?
Solution:
−d ( B)
(i) As, = 1x10 −2 mol L−1 S−1
dt
1 d [ B] 1
∴ Rate = − = x1x10−2 = 0.5x10−2 mol L−1 S−1
2 dt 2
(ii) Rate of change in concentration of A
−d [ A ] 1 d [ B]
= =−
dt 2 dt
= 0.5 x 10-2 mol L-1S-1.
rate change in concentration of C
+ d [ C ] −3 d [ B]
= =
dt 2 dt
3
= x1x10−2
2
= 1.5 x 10-2
[Factors influencing rate of reaction, order and molecularity]

1 MARK QUESTIONS :
1. For a reaction, A + B → Products, the rate law is Rate = k[A][B]3/2. Can the reaction be an
elementary reaction? Explain.
During an elementary reaction, the number of atoms or ions colliding to react is referred to as
molecularity. Had this been an elementary reaction the order of reaction with respect to B would have
3
been 1, but in the given rate law it is . This indicates that the reaction is not an elementary reaction.
2
45
2. For a second order reaction, calculate the units of the rate constant if the concentration is expressed
in atmosphere and time in seconds.
For a second order reaction,
Rate = k[A]2
or atm s = k(atm)2
–1
atm s−1
or k= 2
= atm −1s−1
atm
3. How is rate constant related to concentration of the reactants?

Rate constant of a reaction does not depend on the concentration of the reactants.
4. Can a reaction having the following rate law be an elementary process?

Rate = k[A] [B]1/2
No, this reaction is not an elementary process because elementary process cannot have a fractional
order.
5. Does molecularity have any meaning for a complex reaction?

Molecularity has no meaning for a complex reaction. The concept is applicable to a simple one step
reaction (elementary reactions) or a single step of a complex reaction.
6. What is the molecularity of the given reaction?

1
Cl → Cl2 ( g )
2
Molecularity of the reaction = 1.
7. The reaction, A + 2B → C obeys the rate equation, Rate = k[A]1/2 [B]3/2 What is the order of the
reaction?
1 3
Order of reaction = + = 2
2 2
8. For the reaction A → B, the rate of reaction becomes three times when the concentration of A is
increased by nine times. What is the order of reaction?
Let, r = k [A]n …(i)
Given, 3r = k [9A] n …(ii)
Dividing equation (ii) by (i), we get
3r k [ 9A ] 9n k [ A]
n n
= =
k [ A] k [A]
n n
r
3 = 9n or 31 = 32n
1
⇒ 2n = 1 or n=
2
∴ Rate, r = k[A]1/2
1
Order of reaction =
2

46
9. For which type of reactions, order and molecularity have the same value?
If the reaction is an elementary reaction, order is same as molecularity.
10. Why is the probability of reaction with molecularity higher than three very rare?
The probability of more than three molecules colliding simultaneously is very small. Hence, possibility
of molecularity being three is very low.
11. Why order of reaction may or may not be same as the sum of stoichionetric coefficient of the reacting
species in a balanced chemical equation?
(or)
Why rate law for any reaction cannot be predicted by merely looking at the balanced chemical
equation?
Rate expression is experimental data.
12. Which specie is an intermediate in the reaction

−1
2H 2O2 → I
Alkaline medium
2H 2O + O 2 followed below
Mechanism (1) H 2O 2 + I −1 → H 2O + IO −
(2) H 2O 2 + IO − → H 2O + I − + O 2
Solution:
IO −
13. How order and molecularity are related in a complex reaction for the slowest step?
For a complex reaction molecularity of the slowest step is same as the order of the overall reaction.
2 MARK QUESTIONS :
1. The rate law expression for the reaction
A + B → Products
is, Rate = k[A]1/3 [B]2
i) What is the order of the reaction?
ii) What are the units of rate constant if concentration is measured in mol dm-3 and time in seconds?
Given : Rate = k[A]1/3 [B]2
1 7
Order of reaction = +2=
3 3
Rate
Rate constant, k =
[ A ] [ B]
1/3 2
mol dm −3s −1
=
( mol dm ) ( mol dm )
−3 1/ 3 −3 2
= mol–4/3 dm4 s–1

47
2. When is the rate of reaction equal to specific reaction rate?

Rate reaction can be equal to specific reaction rate under two conditions :
i) When concentration of each of the reactant is 1 mol L-1.
Rate = k[A]α [B]β = k x 1 x 1 = k
ii) Or when the order with respect to each reactant is zero, i.e., the overall order or the reaction is zero.
Rate = k[A]0 [B]0 = k
3. Consider the rate equation for :

H2 + Br2 → 2HBr
Its rate law is :
[H ][ Br2 ]
3/2
Rate = k 2
[HBr]
What is the order of reaction? Write down units of its rate constant if time is taken in seconds.
3 3
Order = 1 + −1 =
2 2
Unit of k = (Mol L-1) 1-n sec-1
3
( mol L ) -1 1- 2
sec -1
1 1
- +
Mol 2 L 2 sec-1
4. The rate law for the reaction Ester + H+ → Acid + Alcohol is :

dx
= k [ Ester ]  H + 
0
dt
What would be the effect on the rate if (i) concentration of the ester is doubled? (ii) concentration of
H+ is doubled?
i) The rate of reaction will be doubled.
ii) No effect on rate.
5. Differentiate between rate of reaction and reaction rate constant.

S. No. Rate of Reaction Reaction Rate Constant
i) Rate of reaction is the change in It is the rate of reaction when the molar
concentration of a reactant or product in a concentration of each of the reactants is
unit interval of time. unity.
ii) The rate of reaction at any instant of time The rate constant does not depend upon
depends upon the molar concentrations of the concentrations of the reactants.
the reactants at that time.
iii) Its units are always mol litre–1 time–1. Its units depend upon the order of
reaction.
48
6. A reaction is of second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is reduced to half? What is the unit of rate constant for such a reaction?
Consider the reaction nR → Products
As the reaction is of second order
∴ Rate, r = k [R]2 ...(i)
If the concentration of the reactant reduced to half, then
2
R 
Rate, r' = k  
2
Dividing equation (ii) by (i), we get
r' k [ R ]
2
1
= =
r 4k [ R ] 2
4
1 1
r' = , i.e., rate of reaction becomes th of the initial rate.
4 4
The unit of rate constant is mol-1 L s-1.
7. What do you understand by the rate law and rate constant of a reaction? Identify the order of a
reaction if the units of its rate constant are:
i) L–1 mol s–1 ii) L mol–1 s–1.
An experimentally determined expression which relates the rate of reaction with the concentration of
reactants is called rate law while the rate of reaction when concentration of each reactant is unity in a
rate law expression is called rate constant.
i) Comparing power of mole in L–1 mol s–1 and (mol L–1)1–n s–1,
We get
1 = l – n ⇒ n = 0 i.e., zero order reaction
ii) Again comparing power of mole in L mol–1s–1 and (mol L-1 )1–n s–1 we get
–1 = 1 – n ⇒ n = 2, i.e., second order reaction
8. Calculate the overall order of a reaction which has the rate expression,
i) Rate = k[A]1/2 [B]3/2 ii) Rate = k[A]3/2 [B]–1
1 3
i) Order = + = 2, i.e., second order.
2 2
3 1
ii) Order = + ( -1) = , i.e., half order.
2 2
49
9. Write two differences between ‘order of reaction’ and ‘molecularity of reaction’.

Ans. Differences between order and molecularity of reaction:
S. No. Order Molecularity
i) It is the sum of the powers of the It is the number of reacting species taking
concentration of the reactants in the rate part in an elementary reaction, which must
law expression. collide simultaneously so as to result into a
chemical reaction.
ii) It is determined experimentally. It is a theoretical concept.
iii) It can be zero or a fraction It cannot be zero or a fraction.
iv) Order is applicable to elementary as well Molecularity is applicable only for
as complex reactions. elementary reactions.
For complex reactions it has no meaning.
10. Consider the decomposition of hydrogen peroxide in alkaline medium which is catalysed by iodide
ions.
-
2H 2 O 2 
OH
→ 2H 2 O + O 2
This reaction takes place in two steps as given below:
Step - I H2O2 + I − → H2O2 + IO − (slow)
Step - II H2O2 + IO − → H2O + I − + O2 (fast)
Solution :
i) Write the rate law expression and determine the order of reaction w.r.t. H2O2.
ii) What is the molecularity of each individual step?
Solution :
i) Rate = k [H2O2]1 [I–]1
Order of reaction w.r.t H2O2 = 1
ii) Molecularity of step I = 2 and step II = 2.
3 MARK QUESTIONS :
1. The gas phase decomposition of nitrous oxide (N2O) is believed to occur via two elementary steps :
Step 1 : N2O k1
→ N2 + O
Step 2 : N 2O + O 
k2
→ N 2 + O2
Experimentally the rate law is found to be Rate = k[N2O]
a) Write the equation for the overall reaction.
b) Which of the species are intermediates?
c) What can you say about the relative rates of steps 1 and 2?
a) Adding the equations of steps 1 and 2 gives the overall reaction
2N 2O → 2N 2 + O2
b) Since O atom is produced in the first step and it does not appear in the overall balanced equation, it
is an intermediate.
c) As rate equation involves one molecule of N2O, we can conclude step – 1 as RDS
∴ Step – 1 is slow step and
Step – 2 fast step
50
2. The rate of reaction, 2NO + Cl2 → 2NOCl is doubled when concentration of Cl2 is doubled and it
becomes eight times when concentration of both NO and Cl2 are doubled. Deduce the order of the
reaction.
Let r = k [NO]x [Cl2]y …(i)
x
2r = k [NO] [2Cl2] y …(ii)
x
8r = k [2NO] [2Cl2] y …(iii)
Dividing (iii) by (ii), we get
8r k [ 2NO] [ 2Cl2 ]
x y
=
k [ NO] [ 2Cl2 ]
x y
2r
22 = [2]x
x=2
Putting the value of x in (i) and (ii), we get
r = k [NO]2 [Cl2]y
2r = k [NO]2 [2Cl2]y
2r [ 2Cl2 ]
y
=
[Cl2 ]
y
r
2 = [2]y
y=1
Rate = k[NO]2 [Cl2]1
Overall order of reaction = x + y = 2 + 1 = 3
3. Following reaction takes place in one step:

2NO(g) + O2(g) → 2NO2(g)
How will the rate of the above reaction change if the volume of the reaction vessel is reduced to one-
third of its original volume? Will there be any change in the order of the reaction with reduced
volume?
Rate = k [NO]2 [O2]
Let initially, moles of NO = a, moles of O2 = b, volume of the vessel = V. Then
Thus, there is no effect on the order of reaction.

51
4. Nitric oxide, NO, reacts with oxygen to produce nitrogen dioxide.

2NO(g) + O2(g) → 2NO2(g)
The rate law for this reaction is:
Rate = k [NO]2 [O2]
Propose a mechanism for the reaction.
Solution :
The probable proposed mechanism may be,
The probable proposed mechanism may be,
NO + O2 ⇌ ΝΟ3 (fast) Step I
NO3 + NO  k1
→ NO2 + NO2 (slow) Step II
Since slowest reaction is the rate determining step, therefore
4 MARK QUESTIONS :
1. Identify the reaction order from the following rate constants :
a) k = 3.1 x 10-4 s-1
b) k = 1.2 x 10-2 atm-1 s-1
c) k = 1.35 x 10-2 mol-2 litre2 s-1
d) k = 3.4 x 10-3 mol-1 litre s-1
a) Let the reaction be of nth order.
∴ [conc.]1-n x Time-1 = Unit of k
1− n
 mol  −1 –1
 litre  x sec = sec
∴ 1 – n = 0,
n = 1, i.e., Reaction is of first order.
b) [atm]1-n x s-1 = atm-1 s-1
∴ 1 – n = –1,
n = 2, i.e., Reaction is of second order.
1− n
 mol 
c)   x sec −1 = mol-2 litre2 sec-1
 litre 
∴ 1 – n = –2,
n = 3, i.e., Reaction is of third order.
1− n
 mol 
d)   x sec −1 = mol-1 litre sec-1
 litre 
∴ 1 – n = –1,
n = 2, i.e., Reaction is of second order.
52
2. The rate of a chemical reaction is expressed either in terms of decrease in the concentration of a
reactant per unit time or increase in the concentration of a product per unit time. Rate of the reaction
depends upon the nature of reactants, concentration of reactants, temperature, presence of catalyst,
surface area of the reactants and presence of light. Rate of reaction is directly related to the
concentration of reactant. Rate law states that the rate of reaction depends upon the concentration
terms on which the rate of reaction actually depends, as observed experimentally. The sum of powers
of the concentration of the reactants in the rate law expression is called order of reaction while the
number of reacting species taking part in an elementary reaction which must collide simultaneously
in order to bring about a chemical reaction is called molecularity of the reaction.
i) Express the rate of the following reaction in terms of different reactants and products.
4NH3(g) + 5O2 (g) → 4NO2(g) + 6H2O(g)
1 d [ NH3 ]
Rate of reaction = –
4 dt
1 d [O 2 ] 1 d [ NO 2 ] 1 d [ H 2 O]
=- =+ =+
5 dt 4 dt 6 dt
ii) Why do pieces of wood burn faster than a log of wood of the same mass?
Pieces of wood have larger surface area than the log of wood of the same mass. Greater the surface
area, faster is the reaction.
iii) Why does the rate of any reaction generally decrease during the course of the reaction?
The rate of reaction depends on the concentration of reactants. As the reaction progresses, reactants
start getting converted to products so the concentration of reactants decreases hence the rate of
reaction decreases.
iv) Why is molecularity applicable only for elementary reactions and order is applicable for
elementary as well as complex reactions?
A complex reaction proceeds through several elementary reactions. Number of molecules involved
in each elementary reaction may be different, i.e., the molecularity of each step may be different.
Therefore, discussion of the molecularity of overall complex reaction is meaningless. On the other
hand, order of a complex reaction is determined by the slowest step in its mechanism and is not
meaningless even in the case of complex reactions.
v) The kinetics of the reaction
mA + nB + pC → m′ X + n′ Y + p′ Z
obey the rate expression dx/dt = k[A]m[B]n
Calculate total order and molecularity of the reaction.
The total order of reaction = m + n
The molecularity of the reaction = m + n + p

53
3. Read the passage given below and answer the following questions:
The progress of the reaction, A ⇌ nB with time is represented in the following figure:
i) What is the value of ‘n’?

ii) Find the value of the equilibrium constant?
iii) The initial rate of conversion of A will be
iv) Which of the following factors has no effect on rate of reaction?
a) Temperature b) Nature of reactant
c) concentration of reactant d) Molecularity
Solution:
n=2
Concentration of A falls from 0.5 to 0.3M in 4 hr (5-1=4hr), while in the same time concentration of B
increases from 0.2 to 0.6M
Decrease in concentration of A in 4 hours, = 0.5 – 0.3 = 0.2M
increase in concentration of B in 4 hours
= 0.6 - 0.2 = 0.4M
Thus, increase in concentration of B in a given time is twice the decrease in concentration of A.
Thus, n = 2
[ B] ( 0.6 )
2 2
ii) K= = = 1.2M
[ A ] 0.3
iii) from t = 0 to t = 1hr
for A, dx = 0.6 - 0.5 = 0.1 mol L-1
dx 0.1mol L−1
initial rate of conversion of A = =
dt 1hr
= 0.1 mol L-1hr-1
iv) The number of reacting species taking part in an elementary reaction is called molecularity and it
has no influence on the rate of reaction
54
5 MARK QUESTIONS :
1. State the order with respect to each reactant, order of overall reaction and the units of rate constant
in each of the following reactions :
a) 2NO + Br2 → 2NOBr.
Rate = k[NO]2 [Br2]
b) CH3CHO(g) → CH4(g) + CO(g).
Rate = k[CH3CHO]3/2
c) 2H2(g) + 2NO(g) → 2H2O(g↑) + N2(g).
Rate = k[H2] [NO]2
d) CO(g) + Cl2(g) → COCl2 (g).
Rate = k[CO]2 [Cl2]1/2
e) H2O2 + 3I– + 2H+ → 2H2O + I3–.
Rate = k[H2O2] [I–]
a) Orders with respect to NO and Br2 are 2 and 1, respectively.
Overall order = 3
1− n 1− 3
 mol   mol 
Units of k =   x sec −1 =  x sec −1
 litre   litre 
= mol–2 litre2 sec-1
3
b) Order =
2
1− n 1− 3/2
Units of k =   x sec −1 =   x sec −1
 litre   litre 
= mol litre sec–1
–1/2 1/2
c) Orders with respect to H2 and NO are 1 and 2 respectively.

Overall order = 1+2 = 3
1− 3
 mol 
Units of k =  x sec −1 = mol–2 litre2 sec–1
 litre 
1
d) Orders with respect to CO and Cl2 are 2 and respectively.
2
1 5
Overall order = 2 + =
2 2
1− n 1− 5/2
Units of k =   x sec −1 =   x sec −1
 litre   litre 
–3/2
= mol litre sec3/2 -1
e) Order with respect to H2O2 and I– are one (first order). Overall order = 1 + 1 = 2
1− n 1− 2
Units of k =   x sec −1 =  x sec −1
 litre   litre 
= mol–1 litre1 sec–1

55
2. Identify the reaction order from each of the following expressions :

a) k = 5.6 x 10-4 mol dm-3 s-1
b) k = 4.5 x 10-3 dm-3 mol-1 s-1
c) k = 3.2 x 10-3 s-1
d) k = 1.6 x 10-2 dm6 mol-2 s-2
e) k = 4 x 10-6 atm-1 s-1
Ans : a) zero b) second c) first d) third e) second
3. For the reaction, 2NO + Cl2 → 2NOCl

at 300 k following data are obtained.
Initial concentration (mol L-1)
Expt. No. Initial rate (mol L-1 s-1)
[NO] [Cl2]
1. 0.010 0.010 1.2 x 10-4
2. 0.010 0.020 2.4 x 10-4
3. 0.020 0.020 9.6 x 10-4
Write rate law for the reaction. What is the order of the reaction? Also calculate the specific rate
constant.
Let the rate law for the reaction be
Rate = k[NO]x [Cl2]y
From Expt. (1), 1.2 x 10-4 = k[0.010]x [0.010]y . . . .(i)
From Expt. (2), 2.4 x 10-4 = k[0.010]x [0.020]y . . . .(ii)
Dividing eqn. (ii) by eqn. (i), we get
2.4 x 10−4 [0.020]
y
=
1.2 x 10−4 [0.010]y
or 2 = (2)y
y=1
From Expt. (2), 2.4 x 10-4 = k[0.010]x [0.020]y . . . .(ii)
From Expt. (3), 9.6 x 10-4 = k[0.020]x [0.020]y . . . .(iii)
Dividing eqn. (iii) by eqn. (ii),
9.6 x 10−4 [0.020]
x
=
2.4 x 10−4 [0.010]x
or 4 = 2x
x=2
Order of reaction = x + y = 2 + 1 = 3
Rate law for the reaction is
Rate = k[NO]2 [Cl2]
Considering eqn. (i) again,
1.2 x 10-4 = k[NO]2 [Cl2]
1.2 x 10−4
k= = 1.2 x 102 mol −2 litre2 sec −1
[0.010]
3

56
4. The following data were obtained for the reaction :

2NO2(g) + F2(g) → 2NO2 F(g)
Expt. No. [NO2] [F2] Initial rate mol L-1 min-1
1. 0.2 0.05 6 x 10-3
2. 0.4 0.05 1.2 x 10-2
3. 0.80 0.10 4.8 x 10-2
Determine the order of reaction and write down the rate law expression.
Let the orders with respect to NO2 and F2 are α and β respectively, the rate law will be :
∴ Rate = k[NO2]α [F2]β
6 x 10-3 = k[0.2]α [0.05]β . . . . (i)
1.2 x 10-2 = k[0.4]α [0.05]β . . . . (ii)
4.8 x 10-2 = k[0.8]α [0.10]β . . . . (iii)
Dividing eqn. (ii) by eqn. (i), we get
2 = [2]α ∴α=1
Dividing eqn. (iii) by eqn. (ii), we get
4 = [2]α [2]β
when α = 1
2 = [2]β ∴β=1
Overall order of reaction = α + β = 2
Rate = k[NO2] [F2]
[Integrated rate equations]

1 MARK QUESTIONS :
1. Reactions of which order will show the rate to be independent of time?
(or)
Is there any reaction whose rate does not fall with the progress of the reaction?
Zero order reactions. In these reactions, the rate is uniform, i.e., the rate is independent of time or
progress of the reaction.
2. If initial concentration of reactant is ‘a’ then calculate the time for 100% completion of zero order
reaction :
For zero order reaction :
x = kt
For 100% completion, x=a
∴ a = kt100%
a
t100% =
k

57
3. A reaction is 50% complete in 2 hours and 75% complete in 4 hours. What is the order of the
reaction?
As t75% = 2t50%
Therefore, it is a first order reaction.
4. Why most of zero order reaction occur on metal surfaces?

(or)
Why decomposition of ammonia on a metal surface is a zero order?
Solution:
At high pressure, the metal surface gets saturated with gas molecules. So, a further change in
reaction conditions is unable to alter the amount of gas on the surface of the catalyst making rate of
the reaction independent of its concentration.
2 MARK QUESTIONS :
1. 87.5% of the substance disintegrated in 45 minutes (first order reaction). What is its half-life?
2. The half-life of a first order reaction is 60 min. How long will it take to consume 90% of the
reactant?
For the first order reaction,
0.693 0.693
k= = = 11.55 x 10 −3 min −1
t1/ 2 60
Applying first order kinetic equation,
2.303 a
t= log
k (a − x )
Given : a = 100, x = 90, i.e., (a – x) = (100 - 90) = 10
2.303
Hence, t = log 10 = 199 min
11.55 x 10−3

58
3. Half-life of a radioactive element is 10 seconds. Calculate its average life. In how much time 75% of
the radioactive element will decay?
Average life τ = t1/2 x 1.44
= 10 x 1.44 = 14.4 sec
Given N0 = 100
N = 100 – 75 = 25
2.303 N 
λ= log  0 
t  N 
0.693 2.303  100 
= log10  
10 t  25 
t = 20 sec
(or)
t75% = 2t1/2
= 2 x 10 sec
= 20 sec
4. For a reaction : 2NH 3 ( g ) 

Pt
→ N 2 ( g ) + 3H 2 ( g )
Rate = k
i) Write the order and molecularity of this reaction.
ii) Write the unit of k.
Solution :
i) Zero order, bimolecular
ii) mol L–1 s–1
5. For a chemical reaction R → P, the variation in the concentration (R) vs. time (t) plot is given
alongside.
i) Predict the order of the reaction.
ii) What is the slope of the curve?
Solution :
i) Order of the reaction is zero.
d [R ]
ii) Slope = = -k
dt

59
6. The rate constant for a reaction of zero order in A is 0.0030 mol L–1 s–1. How long will it take for the
initial concentration of A to fall from 0.10 M to 0.075 M?
k = 0.0030 mol L–1s–1, [R]0 = 0.10 M, [R] = 0.075 M
We know that
[R] = – kt + [R]0
0.075 = – 0.0030t + 0.10
⇒ 3t = 100 – 75 ⇒ t = 8.33 seconds
7. Define the following terms:

i) Pseudo first order reaction
ii) Half life period of reaction (t1/2)
i) A reaction which is not truely of first order but under certain conditions becomes a reaction of first
order is called pseudo first order reaction, e.g., acid hydrolysis of ethyl acetate.
ii) The half life (t1/2) of a reaction is the time in which the concentration of reactant is reduced to one
half of its initial concentration [R]0.
For a reaction: A + H2O → B, Rate ∝ [A].
What is its i) molecularity ii) order of reaction?
i) Pseudo unimolecular and biomolecular
ii) Order = 1.
8. After 24 hrs, only 0.125 gm out of the initial quantity of 1 gm of a radioactive isotope remains behind.
What is its half life period?
Here, [R]0 = 1 g, [R] = 0.125g, t = 24 h

60
9. Rate constant k for first order reaction has been found to be 2.54 × 10–3 s–1. Calculate its three-fourth
life.
Substituting these values in equation (i), we get
10. i) Explain why H2 and O2 do not react at room temperature.

ii) Write the rate equation for the reaction A2 + 3B2 → 2C, if the overall order of the reaction is zero.
Solution :
i) Due to high activation energy for the reaction.
ii) Rate = k[A2]0 [B2]0 or Rate = k
3 MARK QUESTIONS :
1. A first order reaction is 20% completed in 10 minutes. Calculate the time taken for the reaction to go
to 80% completion.
Applying first order equation,
2.303 100
k= log
t (100 − 20 )
2.303 100
= log = 0.0223 min −1
10 80
Again applying first order equation,
2.303 100
t= log
k (100 − 80 )
2.303 100
= log = 72.18 min
0.0223 20

61
2. Initial concentration determines half life of a zero order reaction”. Justify this statement.
For a zero order reaction,
[A0] – [A] = kt
A
When [ A ] = 0 , t = t1/2
2
[ A 0 ] −  0  = kt1/2
A
Hence,
 2
or
[A ]
t1/2 = 0
2k
or t1/2 ∞ [A0]
Thus, half-life period of a zero order reaction is directly proportional to the initial concentration.
3. Half-life and three-fourth life of a first order reaction are t1 and t2 respectively. What is the relation
between them?
0.693
t1/2 (half-life) of a first order reaction =
k
2.303 a
We know that t = log
k a−x
3
When x = a, t = t1
4
2.303 a 2.303 x 2
∴ t1 = log = log 2
k 3 k
a− a
4
2 x 2.303 x 0.30 2 x 0.693
= = = 2 x t1/2 ; t1 = 2t2
k k
4. Observe the graph in diagram and answer the following questions.

i) If slope is equal to –2.0 × 10–6 sec–1, what will be the value of rate constant?
ii) How does the half-life of zero order reaction relate to its rate constant?

62
5. A solution of H2O2 when titrated against KMnO4 solution at different intervals of time gave the
following results:
Time (in minutes) 0 10 20
Volume of KMnO4 (mL) 23.8 14.7 9.1
Show that decomposition of H2O2 is first order reaction.
Since the value of k comes out to be constant in both the cases, therefore the reaction is of first order.
6. Define half-life of a reaction. Write the expression of half-life for

i) zero order reaction and ii) first order reaction.
Solution :
The half life (t1/2) of a reaction is the time in which the concentration of a reactant is reduced to one half
of its initial concentration.
[ R ]0
i) t1/2 for a zero order reaction = = where [R]0 = initial concentration, k = rate constant
2k
0.693
ii) t1/2 for a first order reaction =
k
7. Following data are obtained for the reaction :

1
N 2O5 → 2NO2 + O2
2
Time (in seconds) 0 300 600
[N2O5] (mol L–1) 1.6×10–2 0.8×10–2 0.4×10–2
i) Show that it follows first order reaction.

ii) Calculate the half-life.
(Given log 2 = 0.3010, log 4 = 0.6021)
Solution :

63
k is constant and is equal to 2.31 x 10–3 s–1 when we use first order equation. Hence, it follows first order
reaction.
238 206
8. 92 U changes to 92 Pb by successive radioactive decay. A sample of uranium ore was analysed and
238 206 238

found to contain 1.0g of U and 0.1g of Pb had accumulated due to decay of U , find out the
238
age of the ore. (Half-life of U = 4.5 x 109 years)

64
9. The following date were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume:
SO2Cl 2 ( g ) → SO 2( g ) + Cl 2( g )
Experiment Time (s) Total pressure (atm)
1 0 0.4
2 100 0.7
Calculate the rate constant
(Given : log4 = 0.6021, log2 = 0.301)
2.303 Po
K= log
t 2Po − Pt
Here Po = 0.4 atm, t = 100s, pt = 0.7 atm
2.303 0.4
K= log
100 2 ( 0.4 ) − 0.7
2.303 0.4
= log
100 0.1
2.303 2.303
= log 4 = ( 0.6021)
100 100
K = 1.386 x 10–2S–1
4 MARK QUESTIONS :
1. For a first order reaction, calculate the ratio between the time taken to complete one-half of the
reaction and the time taken to complete one-third of the reaction :
We know
2.303  a 
k= log10  
t a−x
time taken to complete half of reaction :
t1/2 = 0.693 / k . . . .(i)
rd
Similarly time taken for 1/3 completion of reaction will be :
2.303  a 
t1/ 3 = log10 
t  a − a / 3 
2.303  3
= log   . . . .(ii)
k  2
Dividing eqn. (i) by eqn. (ii) we get
t1/2 0.693 / k
= = 1.71
t1/3 2.303 log 3 / 2
k
65
2. Read the passage given below and answer the following questions:
∆
The following reaction, A ( g )  → P( g ) + Q ( g ) + R ( g ) , follows first order kinetics. The half life period
of this reaction is 69.3 s at 500oC. The gas ‘A’ is enclosed in a container at 500oC and at a pressure
of 0.4 atm.
(i) The rate constant for the reaction is ____________
(ii) The pressure of the gas ‘A’ after 230s will be ____________
(iii) The total pressure of the system after 230s will be ____________
(iv) The plot of ln[A] vs t will be ____________
Solution:
0.693 0.693
(i) K = = = 0.01S−1
t1/2 69.3
2.303 a 2.303 0.4

(ii) K = log ⇒ 0.01 = log
t a−x 230 0.4 − x
0.01 0.4
= log
0.01 0.4 − x
0.4
10l = ⇒ x = 0.36
0.4 − x
PA = a − x = 0.4 − 0.36 = 0.04atm
∆
(iii) A(g)  → P(g) + Q(g) + R(g)
Pi 0.4 0 0 0
Pt 0.4 - 0.36 0.36 0.36 0.36
PTotal = 0.4 - 0.36 + 0.36 + 0.36 + 0.36 = 1.12 atm
ln [ A ]t = ln [ A ]o − kt
(iv)
y = C + mx

66
5 MARK QUESTIONS :
1. Consider the reaction R  k
→ P . The change in concentration of R with time is shown in the
following plot:
i) Predict the order of the reaction.
ii) Derive the expression for the time required for the completion of the reaction.
iii) What does the slope of the above line indicate?
Solution :
i) The reaction R → P is a zero order reaction.
ii)
-d [ R ]
rate = =k
dt
d [R] = –k dt
Integrating both sides,
[R] = –kt + C. where C = constant of integration . . . . (i)
At t = 0, [R] = [R]0
Substituting this in equation (i)
C = [R]0
Substituting the value of C is equation (i)
[R] = –kt + [R]0
kt = [R]0 – [R]
[ R ]0 - [ R ]
⇒ t=
k
On completion of reactions, [R] = 0
[ R ]0
t=
k
iii) From equation (ii), we have slope of curve
d [R ]
Slope = = = -k
dt
2. For a certain chemical reaction variation in the concentration ln [R] vs. time plot is given alongside.
For this reaction
i) What is the order of the reaction?
ii) What are the units of rate constant k?
iii) Give the relationship between k and t1/2 (half-life period).
iv) What is the slope of the curve?
v) Draw the plot log [R]0 / [R] vs time t(s).
Solution :
0.693
i) First order ii) time–1 (s–1) iii) k = iv) slope = – k (rate constant)
t1/2
v)

67
3. Nitrogen pentoxide decomposes according to equation:

2N2O5(g) → 4NO2(g) + O2(g)
This first order reaction was allowed to proceed at 40°C and the data below were collected:
i) Calculate the rate constant. Include units with your answer.

ii) What will be the concentration of N2O5 after 100 minutes?
iii) Calculate the initial rate of reaction.

68
4. For the hydrolysis of methyl acetate in aqueous solution, the following results were obtained:
i) Show that it follows pseudo first order reaction, as the concentration of water remains constant.
ii) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
(Given log 2 = 0.3010, log 4 = 0.6021)
Solution :
5. i) Write the rate law for a first order reaction. Justify the statement that half life for a first order
reaction is independent of the initial concentration of the reactant.
ii) The activation energy of a reaction is 75.2 kJ mol–1 in the absence of a catalyst and it lowers to
50.14 kJ mol–1 with a catalyst. How many times will the rate of reaction grow in the presence of a
catalyst if the reaction proceeds at 25°C?
Solution :
i) Consider the first order reaction,
R→P
For this reaction, rate law which relates the rate of reaction to the concentration of reactants can be
given as
-d [ R ]
Rate = = k [R ]
dt
69
For a first order reaction,

2.303 [ R ]0
t= log , where [R]0 = initial concentration, [R] = concentration at time t.
k [R ]
At t1/2, [R] = [R]0 / 2
So, the above equation becomes
2.303 [ R ]0
t1/2 = log
k [ R ]0 / 2
2.303 2.303
t1/2 = log 2 or t1/2 = x 0.3010
k k
0.693
t1/2 =
k
This shows that half life of a first order reaction is independent of the initial concentration of the
reactant.
ii) According to Arrhenius equation,
Ea
log k = log A -
2.303 RT
For uncatalysed reaction, For catalysed reaction,
Ea Ea
log k1 = log A - . . . (i) log k 2 = log A - . . . (ii)
2.303 RT 2.303 RT
A is equal for both reactions.
Subtracting equation (i) from equation (ii),
log
k2
=
E a1 - E a 2
=
( 75.2 - 50.14 ) kJ mol-1 = 4.39
k1 2.303RT 2.303 x 8.314JK -1 mol-1 x 298K
k2
= antilog (4.39) = 2.45 x 104
k1
Rate of reaction increases by 2.45 × 104 times.
[Temperature dependence of reaction, effect of catalyst, collision theory]

1 MARK QUESTIONS :
1. Hydrogen and oxygen do not react at room temperature. Why?
At room temperature, there is no reaction between hydrogen and oxygen as the activation energy of the
reaction is very high.
2. Slow reactions require less activation energy as compared to fast reactions. Do you agree with this
statement?
No, because rate of reaction is inversely proportional to activation energy.
70
3. In some cases, it is found that a large number of colliding molecules have energy more than threshold
energy, yet the reaction is slow. Why?
Reaction rate of such reactions will be slow because of improper collision among reactant molecules.
4. Why does the rate of a reaction increase with rise in temperature?

At higher temperatures, larger fraction of colliding particles can cross the energy barrier (i.e., the
activation energy), which leads to faster rate.
5. What is the effect of adding a catalyst on

i) Activation energy (Ea), and ii) Gibbs energy (∆G) of a reaction?
i) Decreases ii) No effect
2 MARK QUESTIONS :
1. Can a reaction have zero activation energy?
We know that k = Ae − Ea /RT .
When E = 0, the expression becomes
k = A x e0 = A
i.e., Rate constant = Collision frequency
This implies that every collision is an effective collision and leads to product formation which is not
possible. Thus, activation energy cannot be zero.
2. What is the value of rate constant at extremely high temperature (T = ∞). Is this rate constant
possible?
We know that, k = Ae − Ea /RT
When T = ∞, k = A.
i.e., the rate constant approaches frequency factor which is not possible.
3. Temperature coefficient of a reaction is 2. By what factor, the rate will increase if there is 100oC rise
in temperature?
We know that
( Rate )T
= (µ)
2
∆T /10
( Rate )T 1
Where µ is the temperature coefficient = 2100/10 = 210 = 1024

i.e., rate increases by 1024 times.

71
1
4. A graph between ln k and for a reaction is given.
T
Here k is rate constant and T is temperature in kelvin.
If OA = a and OB = b, answer the following:
i) What is the activation energy (Ea) of the reaction?
ii) What is the frequency factor (A) for the reaction?
5. Answer the following questions on the basis of the given plot of potential energy vs reaction
coordinate:
i) What is the threshold energy for the reaction?
ii) What is the activation energy for forward reaction?
iii) What is the activation energy for backward reaction?
iv) What is enthalpy change for the forward reaction?
Solution :
i) Threshold energy for the reaction = 300 kJ mol–1
ii) Activation energy for the forward reaction = 300 – 150 = 150 kJ mol–1
iii) Activation energy for the backward reaction = 300 – 100 = 200 kJ mol–1
iv) Enthalpy change for the forward reaction ∆rH = 100 – 150 = – 50 kJ mol–1
3 MARK QUESTIONS :
1
1. Give the nature of plot when k is plotted against T and log k is plotted against .
T
We know, k =Ae–Ea / RT . . . . . (i)
Its logarithmic form is :
Ea 1
log10 k = log10 A − x . . . . . (ii)
2.303 R T

72
From equation (i) rate constant ‘k’ will exponentially increase with temperature.
From equation (ii) plot of log10 k against 1/T will be a straight line :
2. The rate constant for the first order decomposition of H2O2 is given by the following equation:
1.0 x 104
logk = 14.2 - K
T
Calculate Ea for this reaction and rate constant k, if its half-life period be 200 minutes.
(Given: R = 8.314 JK–1 mol–1)
1.0 x 104 Ea
Comparing the equation, log k = 14.2 - K with the equation log k = log A - ,
T 2.303RT
3. The rate constant of a first order reaction increases from 2 × 10–2 to 4 × 10–2 when the temperature
changes from 300 K to 310 K. Calculate the energy of activation (Ea).
(log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021)
Substituting k1 = 2×10 , k2 = 4×10 , T1 = 300 K, T2 = 310 K, R 8.314 J K-1 mol-1 in the expression

73
4. For a reaction, the energy of activation is zero. What is the value of rate constant at 300 K, if
k = 1.6 × 106 s–1 at 280 K? [R = 8.31 J K–1 mol–1]
Given T1 = 280 K, k1 = 1.6 × 106 s–1, k2 = ?, Ea = 0, T2 = 300 K.
By Arrhenius equation,
Thus, the rate constant at 300 K is 1.6 × 106 s–1.
5. A first order reaction is 50% completed in 40 minutes at 300 K and in 20 minutes at 320 K. Calculate
the activation energy of the reaction.
(Given: log 2 = 0.3010, log 4 = 0.6021, R = 8.314 J K–1 mol–1)
Solution :

74
4 MARK QUESTIONS :
1. The rate constants of a reaction at 700 K and 760 K are 0.011 M −1 sec-1 and 0.105 M −1 sec-1
respectively. Calculate the value of Arrhenius parameter. log(0.011) = –1.958
k1 = 0.011 M–1 sec–1, k2 = 0.105 M–1 sec–1
T1 = 700 K, T2 = 760 K
Substituting these values in the following equation, we get
k  Ea  1 1 
log  2  =  − 
 k1  2.303R  T1 T2 
 0.105  Ea  1 1 
log  =  − 
 0.011  2.303 x 8.314  700 760 
E = 166341 J/mol = 166.34 kJ / mol
Ea
We know, log k = log A −
2.303RT
166341
∴ log 0.011 = log A −
2.303 x 8.341 x 700
–1.958 = log A – 12.41
A = 2.82 x 1010 M–1 sec–1
2. Temperature has a marked effect on the rate of reaction. For most of the reactions,the rate of
reaction becomes nearly double for every 10 degree rise in temperature. The effect of temperature is
usually expressed in terms of temperature coefficient. The quantitative dependence of reaction rate on
temperature was first explained by Swante Arrhenius. Arrhenius proposed a simple equation known
as Arrhenius equation
k = Ae− Ea /RT
This equation provides a relationship between the rate constant (k) of a reaction and the temperature
of the system. A is the Arrhenius factor or pre-exponential factor, Ea is the activation energy and R is
the gas constant.
i) Define ‘activation energy’ of a reaction.
The energy required to form the intermediate called activated complex is known as activation
energy. Activation energy = Threshold energy – Average energy of the reactants
ii) How does a catalyst affect the rate of a reaction? Explain with respect to the Arrhenius equation.
A catalyst decreases the activation energy. According to Arrhenius equation, lower the activation
energy, greater will be the rate constant and thus the rate of reaction increases.
75
iii) Can a reaction have zero activation energy? Justify.

No, Ea ≠ 0.
If Ea = 0, then according to Arrhenius equation,
k = Ae− Ea /RT
k = Aeo = A,
i.e., Rate constant = Collision frequency
This means every collision results into a chemical reaction which cannot be true.
iv) The plot of log k vs X is linear with slope = – Ea / 2.303R. What is X?
1/T
v) What is the fraction of molecules having energy greater than activation energy, Ea?
e− Ea /RT at temperature T.
5 MARK QUESTIONS :
1. The rate constant of a reaction increases by 7% when its temperature is raised from 300 K to 301 K
while its equilibrium constant increases by 3%. Calculate the activation energy of the forward and
the reverse reactions. log(106) = 2.025
We know,
k  Ef  1 1 
log  2  =  −  ....(i)
 k1  2.303R  T1 T2 
k1 = 100, k2 = 107, T1 = 300K, T2 = 301K
Substituting these values in eqn. (i), we get
 107  Ef  1 1 
log  =  − 
 100  2.303 x 8.314  300 301 
Ef = 50804 J mol-1 = 50.804 kJ mol-1
k  ∆H  1 1 
We know, log  2  =  −  ...(ii)
 k1  2.303R  T1 T2 
k2 = 103, k1 = 100, Ti = 300 K, T2 = 301 K
Substituting these values in eqn. (ii), we get
103 ∆H  1 1 
log =  − 
100 2.303 x 8.314  300 301 
∆H = 22195 J mol-1
= 22.195 kJ mol-1
∆H = (Ef – Eb)
= Activation energy of forward reaction – Activation energy of reverse reaction
22.195 = 50.804 – Eb
Eb = 28.609 kJ mol-1

76
NCERT INTEXT QUESTIONS
1. For the reaction R → P the concentration of a reactant changes from 0.03 M to 0.02 M in 25
minutes. Calculate the average rate of reaction using units of time both in minutes and seconds.
Solution :
2. In a reaction 2A → Products, concentration of A decreases from 0.5 mol L–1 to 0.4 mol L–1 in 10
minutes. Calculate the rate during this interval.
Solution :
Rate of reaction = Rate of disappearance of A
1 ∆ [A] 1 ( 0.4 - 0.5 ) mol L
-1
=- =- = 0.005 mol L-1 min -1

2 ∆t 2 10 min
3. 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?
Solution :
1 5
Order of reaction = +2=
2 2
4. The conversion of molecule X to Y follows second order kinetics. If concentration of X is increased to

three times, how will it affect the rate of formation of Y ?
Solution :
Rate = k [X]2
r1 = k [X]2 ...(i)
r2 = k [3X]2 ...(ii)
r2 9k [ X ]
2
Dividing (ii) by (i),
=
k [X]
2
r1
r2 = 9r1
Thus, rate of formation of Y will increase by nine times.

77
5. A first order reaction has a rate constant 1.15 × 10–3 s–1. How long will 5 g of this reactant take to
reduce to 3 g?
Solution :
Given [R]0 = 5 g, [R] = 3g, k = 1.15×10-3s-1. As the reaction is of first order,
= 2.0 × 103 × 0.2219 s = 443.8 s = 444 s
6. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the decomposition is
a first order reaction, calculate the rate constant of the reaction.
For a first order reaction, k = 0.693 = 0.693 = 1.155 x 10-2 min -1
t1/2 60 min
7. What will be the effect of temperature on rate constant?

The rate constant of a reaction is nearly doubled with rise in temperature by 10°. The exact dependence
of the rate constant on temperature is given by Arrhenius equation, k = Ae-Ea /RT where A is called
frequency factor and Ea is the activation energy of the reaction.
8. The rate of the chemical reaction doubles for an increase of 10 K in absolute temperature from
298K.
Calculate Ea.
9. The activation energy for reaction, 2HI(g)→ H2(g) + I2(g), is 209.5 kJ mol–1 at 581 K. Calculate the
fraction of molecules of reactants having energy equal to or greater than activation energy.
Fraction of molecules having energy equal to or greater than activation energy,

78
NCERT TEXTBOOK EXERCISES

1. From the rate expression for the following reactions, determine their order of reaction and the
dimensions of the rate constants:
Solution :
2. For the reaction 2A + B → A2B, the rate = k [A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the
initial rate of the reaction when [A] = 0.1 mol L–1 and [B] = 0.2 mol L–1. Calculate the rate of reaction
after [A] is reduced to 0.06 mol L–1.
Solution :
Initial rate = k [A][B]2 = (2.0 × 10–6 mol–2 L2 s–1) (0.1 mol L–1) (0.2 mol L–1)2
= 8 × 10–9 mol L–1 s–1
When [A] is reduced from 0.10 mol L–1 to 0.06 mol L–1, i.e., 0.04 mol L–1 of A has reacted,
1
B reacted = x × 0.04 mol L–1 = 0.02 mol L–1
2
Now [B] = 0.2 – 0.02 = 0.18 mol L–1
Rate = (2.0 × 10–6 mol–2 L2 s–1) (0.06 mol L–1) (0.18 mol L–1)2
= 3.89 × 10–9 mol L–1 s–1

79
3. The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of
production of N2 and H2 if k = 2.5 × 10–4 mol L–1 s–1?
4. 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.,
3/ 2
Rate = k  PCH 3OCH 3 
If the pressure is measured in bar and time in minutes, then what are the units of rate and rate
constant?
Solution :
In terms of pressure, unit of rate = bar min–1
5. 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 to half?
Rate = k [A]2 = ka2

80
6. What is the effect of temperature on the rate constant of a reaction? How can this effect of
temperature on rate constant be represented quantitatively?
The rate constant of a reaction increases with increase in temperature and becomes nearly double for
every 10°C rise of temperature. The effect can be represented quantitatively by Arrhenius equation,
k = Ae-Ea /RT where Ea is the activation energy of the reaction and A is the frequency factor.
7. In a pseudo first order hydrolysis of an ester in water, the following results were obtained:
Calculate the average rate of reaction between the time interval 30 to 60 seconds.
Solution :
Average rate of reaction between the interval 30–60 s.
8. 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 of B three times?
iii) How is the rate affected when concentration of both A and B are doubled?
-d [ R ]
= k [ A ][ B]
2
i) Rate =
dt
ii) If the concentration of B is tripled, then
Rate = k[A] [3B]2 = 9k[A] [B]2 , i.e., the rate of reaction becomes 9 times.
iii) If the concentration of both A and B are doubled, then
Rate = k[2A] [2B]2 = 8k[A] [B]2 , i.e., the rate of reaction becomes 8 times.
9. 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:

81
What is the order of reaction with respect to A and B?

Let the rate law be r0 = k[A]m [B]n
(r0)1 = 5.07 × 10–5 = k (0.20)m (0.30)n ...(i)
(r0)2 = 5.07 × 10–5 = k (0.20)m (0.10)n ...(ii)
(r0)3 = 1.43 × 10–4 = k (0.40)m (0.05)n ...(iii)
Thus, order of reaction w.r.t. A = 1.5 and order of reaction w.r.t. B = 0.
10. The following results have been obtained during the kinetic studies of the reaction:
2A + B → C + D
Determine the rate law and the rate constant for the reaction.
Solution :
Suppose order of reaction w.r.t. reactant A is m and with respect to B is n. Then the rate law will be
Rate = k [A]m [B]n
Substituting the values of experiments I to IV, we have
(Rate)expt I = 6.0 × 10–3 = k (0.1)m (0.1)n ...(i)
(Rate)expt II = 7.2 × 10–2 = k (0.3)m (0.2)n ...(ii)
(Rate)expt III = 2.88 × 10–1 = k (0.3)m (0.4)n ...(iii)
(Rate)expt IV = 2.4 × 10–2 = k (0.4)m (0.1)n ...(iv)

82
∴ Rate law expression is given by

Rate = k [A] [B]2
Order of reaction w.r.t. A = 1;
Order of reaction w.r.t. B = 2.
Overall order of reaction = 1 + 2 = 3
= 6.0 mol–2 L2 min–1
11. The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in
the blanks in the following table:
Solution :

83
12. Calculate the half-life of a first order reaction from their rate constants given below:
i) 200 s–1 ii) 2 min–1 iii) 4 years–1
Solution :
13. The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood
had only 80% of the 14C found in a living tree. Estimate the age of the sample.
Radioactive decay follows first order kinetics.
14. The experimental data for the decomposition of N2O5

[2N2O5 → 4NO2 + O2]
in gas phase at 318 K are given below:
t(s) 0 400 800 1200 1600 2000 2400 2800 3200
102 x [N2O5] / mol L-1 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 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 rate law?
v) Calculate the rate constant.
vi) Calculate the half-life period from k and compare it with (ii).
Solution :
t(s) 0 400 800 1200 1600 2000 2400 2800 3200
2
10 x [N2O5] / mol L -1 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35
log [N2O5] -1.79 -1.87 -1.94 -2.03 -2.11 -2.19 -2.28 -2.37 -2.46
84
i) Plot of [N2O5] versus time
ii) Initial concentration of [N2O5] = 1.63 × 102 M

Half of the concentration = 0.815 × 102 M
Time corresponding to this concentration = 1450 s. Hence, t1/2 = 1450 s.
iii) Plot of log [N2O5] versus time
iv) As plot of log [N2O5] vs time is a straight line, hence it is a reaction of first order.
∴ Rate law is,
Rate = k [N2O5]
0.693 0.693
vi) t1/2 = = = 1438s
k 4.82 x 10-4 s-1
The two values are almost same within limits of possible error.

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15. 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?
16. During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1 µg of 90Sr was
absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after 10
years and 60 years if it is not lost metabolically?
As radioactive disintegration follows first order kinetics,
17. For a first order reaction, show that time required for 99% completion is twice the time required for
the completion of 90% of reaction.
For a first order reaction,
When the reaction is 99% completed, [R] = [R]0 – 0.99 [R]0 = 0.01 [R]0
When the reaction is 90% completed, [R] = [R]0 – 0.9[R]0 = 0.1[R]0
Hence, t99% = 2t90%

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18. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
For a first order reaction
19. For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data are
obtained:
Calculate the rate constant.

87
20. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume:
SO2Cl2 (g) → SO2 (g) + Cl2 (g)
Calculate the rate of reaction when total pressure is 0.65 atm.

Solution :
21. The rate constant for the decomposition of N2O5 at various temperatures is given below:
Draw a graph between ln k and 1/T and calculate the values of A and Ea. Predict the rate constant at
30°C and 50°C.
Solution :
1
Two draw the graph of ln k versus , we can re-write the given data as follows :
T

88
The value of rate constant at two different temperatures can be determined as follows:

89
22. The rate constant for the decomposition of hydrocarbons is 2.418 × 10–5 s–1 at 546 K. If the energy of
activation is 179.9 kJ/mol, what will be the value of pre-exponential factor?
Given, k = 2.418 × 10–5 s–1, Ea = 179.9 kJ mol–1, T = 546 K.
23. Consider a certain reaction A → Products with k = 2.0 × 10–2 s–1. Calculate the concentration of A
remaining after 100 s if the initial concentration of A is 1.0 mol L–1.
24. Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law
with t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours?
Since sucrose decomposes according to first order rate law,

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25. The decomposition of hydrocarbon follows the equation: k = (4.5 × 1011 s–1) e– (28000 K)/T.
Calculate Ea.
From Arrhenius equation, k = Ae-Ea /RT
26. The rate constant for the first order decomposition of H2O2 is given by the following equation:
log k = 14.34 – 1.25 × 104 K/T
Calculate Ea for this reaction and at what temperature will its half-period be 256 minutes.
Substituting the value of k in given equation, we get

91
27. The decomposition of A into product has value of k as 4.5 × 103 s–1 at 10°C and energy of activation
is 60 kJ mol–1. At what temperature would k be 1.5 × 104 s–1?
Solution :
k1 = 4.5 × 103 s–1, T1 = 10 + 273 K = 283 K; k2 = 1.5 × 104 s–1, T2 = ?, Ea = 60 kJ mol–1
From Arrhenius equation,
28. The time required for 10% completion of a first order reaction at 298 K is equal to that required for
its 25% completion at 308 K. If the value of A is 4 × 1010 s–1, calculate k at 318 K and Ea.
Solution :

92
Calculation of k at 318 K:
= 10.6021 – 12.5843 = – 1.9822

or k = Antilog (– 1.9822) = Antilog (2.0178)
= 1.042 × 10–2 s–1
29. The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. Calculate the
energy of activation of the reaction assuming that it does not change with temperature.
Solution :

93
3. ELECTROCHEMISTRY
[Electrolytic solutions, measurement of κ(Conducitivity), variation of κ, Λm]
1 MARK QUESTIONS :
1. What is meant by cell constant?
Cell constant is the ratio of distance (l) between electrodes and area of cross-section (A). It is denoted
l
by . Its unit is cm-1 or m-1.
A
2. Why does the conductivity of a solution decrease with dilution? (NCERT Intext Q.No:2.7)
Conductivity of a solution is the conductance of ions present in a unit volume of the solution. On
dilution, the number of ions per unit volume decreases. So, the conductivity also decreases.
3. Define specific conductance or conductivity. (Exercise Q.No:7)

Specific conductance is defined as conductance of electrolyte when distance between electrodes is 1 cm
and area of cross section is 1 cm2.
4. How is the unit of molar conductivity arrived at?
5. Write the equation showing the relationship between equivalent or molar conductance and
concentration of a strong electrolyte.
Debye-Huckel-Onsager equation, Λ = Λo– b c in which Λ is the molar conductance at concentration c

and b is the constant, Λo is the conductance at infinite dilution.
6. Write the mathematical expression for Kohlrausch’s law.
are the number of cations and anions respectively in one formula
unit of the compound.

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7. Why is alternating current used for measuring resistance of an electrolytic solution? (Exemplar)
Alternating current is used to prevent electrolysis so that concentration of ions in the solution remains
constant.
8. In an aqueous solution how does specific conductivity of electrolytes change with addition of water?
Specific conductivity decreases because number of ions per unit volume decreases by addition of water
or dilution.
9. Solutions of two electrolytes 'A' and,'B'are diluted, The Λ 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. (Exemplar)
Electrolyte 'B' is stronger than 'A' because in 'B' the number of ions remains the same on dilution, but
only interionic attraction decreases. Therefore, Λ m increases only 1.5 times.
2 MARK QUESTIONS :
1. Express the relation among cell constant, resistance of the solution in the cell and conductivity of the
solution. How is molar conductivity of a solution related to its conductivity?
I
Conductivity (κ) = x Cell constant
Resistance ( R )
Conductivity ( κ) x1000
Molar conductivity ( Λ m ) =
Molarity ( M )
2. State Kohlrausch law of independent migration of ions. Why does the conductivity of a solution
decrease with dilution?
Kohlrausch law states that the limiting molar conductivity of an electrolyte can be represented as the
sum of the individual contributions of cation and anion of the electrolyte.
In general, if an electrolyte on dissociation gives ν+ cations and ν– anions then its limiting molar
conductivity is given by
where, λ o+ and λ o− are the limiting molar conductivities of cations and anions respectively.
Conductivity of a solution decreases with dilution. This is due to the fact that the number of ions per
unit volume that carry the current in a solution decreases with dilution.

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3. The conductivity of 0.20M solution of KCl at 298 K is 0.0248 S cm-1. Calculate its molar conductivity.
(Exercise Q.No:8)(CBSE Delhi 2008).
4. The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500Ω. What is the
cell constant if conductivity of 0.001 M KCl solution at 298K is 0.146 x 10-3 S cm-1? (Exercise Q.No:9)
(CBSE Delhi 2008).
5. The electrical resistance of a column of 0.05M NaOH solution of diameter 1 cm and length 50cm is
5.55 x 103 ohm. Calculate its resistivity, conductivity and molar conductivity. (CBSE (AI) 2012).
6. Λm for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0S cm2 mol-1 respectively. Calculate Λ om for
HAc.
Λom(HAc)

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7. Why on dilution the ∧m of CH3COOH increases drastically, while that of CH3COONa increases
gradually? (Exemplar)
In case of CH3COOH, which is a weak electrolyte, the number of ions increase on dilution due to an
increase in degree of dissociation. CH3COOH + H2O → CH3COO- + H3O+.
In case of strong electrolyte the number of ions remains same but the interionic attraction decreases.
8. Define the following terms:

i) Molar conductivity (∧m) ii) Secondary batteries
i) Molar conductivity, ∧m of a solution at a dilution V is defined as the conductance of all the ions
produced from one gram mole of the electrolyte dissolved in V cm3 of the solution when the
electrodes are one centimetre apart and the area of the electrodes is so large that the whole of the
solution is contained between them.
κ x 1000
Λ m = κ x V or Λ m =
Molarity
where, κ is the conductivity and V is the volume of the solution containing 1 mole of the electrolyte.
ii) Secondary batteries are those batteries which can be recharged by passing electric current through
them and hence can be used over again e.g., lead storage battery.
9. Calculate the degree of dissociation (α) of acetic acid if its molar conductivity (∧m) is 39.05 S cm2
mol-1. Given λ oH + = 349.6 S cm 2 mol-1 and λ oCH COO- = 40.9 S cm 2 mol-1
( ) ( 3 )
10. Suggest a way to determine the Λ om for water. (Intext Q.No:2.8)
The molar conductance of water at infinite dilution can be obtained from the knowledge of molar
conductances at infinite dilution of sodium hydroxide, hydrochloric acid and sodium chloride (all strong
electrolytes). This is in accordance with Kohlrausch's law.
Λ om( H2O) = Λ om( NaOH ) + Λ om( HCl ) − Λ om( NaCI )

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3 MARK QUESTIONS :
1. a) State Kohlrausch law of independent migration of ions. Write an expression for the molar
conductivity of acetic acid at infinite dilution according to Kohlrausch law.
b) Calculate Λ om for acetic acid.
Given that Λ om (HCl) = 426 S cm2 mol -1, Λ om (NaCl) = 126 S cm2 mol-1
Λ om (CH3COONa) = 91 S cm2 mol-1
a) Kohlrausch law states that the limiting molar conductivity of an electrolyte can be represented as the
sum of the limiting molar conductivities of individual cation and anion of the electrolyte.
In general, if an electrolyte on dissociation gives ν+ cations and ν– anions then its limiting molar
conductivity is given by
where, λ o+ and λ o− are the limiting molar conductivities of cations and anions respectively.
Conductivity of a solution decreases with dilution. This is due to the fact that the number of ions per
unit volume that carry the current in a solution decreases with dilution.
= Λ om ( CH3COONa ) + Λ om ( HCl) − Λ om ( NaCl)

= (91 + 426 – 126) S cm2 mol-1 = 391 S cm2 mol–1
2. Discuss variation with concentration of conductivity and molar conductivity. (Exercise Q.No:2.7)
Variation of Conductivity and Molar Conductivity with Concentration : Conductivity always decreases
with the decrease in concentration both, for weak and strong electrolytes. This is because the number of
ions per unit volume that carry the current in a solution decreases on dilution. The conductivity of a
solution at any given concentration is the conductance of one unit volume of solution kept between two
platinum electrodes with unit area of cross section and at a distance of unit length. This is clear from the
equation :

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(both A and l are unity in their appropriate units in m or cm).
Molar conductivity of a solution at a given concentration is the conductance of the volume V of solution
containing. One mole of electrolyte kept between two electrodes with the area of cross section A and
distance of unit length. Therefore,
Since l = 1 and A = V (volume containing 1 mole of electrolyte)

κ x 1000
Λm = κ x V =
c
Molar conductivity increases with the decrease in concentration. This is because the total volume, V, of
solution containing one mole of electrolyte also increases. lt has been found that decrease in κ on
dilution of a solution is more than compensated by increase in its volume.
3. 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 λ0(H+) = 349.6 S cm2 mol-1 and λ0(HCOO-) = 54.6 S
cm2 mol-1. (NCERT Intext Q.No:2.9)
Λ 0m ( HCOOH ) = λ 0 ( H + ) + λ 0 ( HCOO- ) = 349.6 + 54.6 = 404.2 S cm 2 mol-1
λm 46.1
α= 0
= = 0.114 ⇒ α = 11.4%
λ m 404.2
Cα 2 0.025 x ( 0.114 )
2
Ka = =
1- α 1- 0.114
0.025 x 0.114 x 0.114
= = 3.67 x 10-4
0.886
4. Conductivity of 2.5 × 10–4 M methanoic acid is 5.25 × 10–5 S cm–1. Calculate its molar conductivity
and degree of dissociation.
Given: λo(H+) = 349.5 S cm2 mol –1 and λo(HCOO–) = 50.5 S cm2 mol –1.

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5. a) Following reactions occur at cathode during the electrolysis of aqueous silver chloride solution:
(CBSE (AI) 2005)
Ag+(aq) + e– → Ag(s) Eo = + 0.80 V
1
H+(aq) + e– → H2 ( g ) Eo = 0.00V
2
On the basis of their standard reduction electrode potential (Eo) values, which reaction is feasible
at the cathode and why?
b) Define limiting molar conductivity. Why conductivity of an electrolyte solution decreases with the
decrease in concentration? (CBSE (Delhi) 2015)
a) The reaction, Ag+(aq) + e– → Ag(s) is feasible at cathode as cathodic reaction is one which has
higher standard reduction electrode potential ( E ored ) .
b) The value of molar conductivity when the concentration approaches zero is known as limiting molar
conductivity. Conductivity of an electrolytic solution decreases with decrease in concentration as
the number of ions per unit volume that carry the current in the solution decrease with decrease in
concentration.
4 MARK QUESTIONS :
1. i) Define the following terms:
a) Limiting molar conductivity b) Fuel cell
ii) Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 Ω. If the resistance of
the same cell when filled with 0.02 mol L–1 KCl solution is 520 Ω, calculate the conductivity and
molar conductivity of 0.02 mol L–1 KCl solution. The conductivity of 0.1 mol L–1 KCl solution is
1.29 × 10–2 Ω–1 cm–1.
i) a) The limiting (maximum) value of molar conductivity when concentration approaches to zero is
called limiting molar conductivity.
b) A fuel cell is a device which converts energy produced during the combustion of fuels like
hydrogen, methane, methyl alcohol etc. directly into electrical energy. One such successful fuel
cell is hydrogen-oxygen fuel cell.
ii) For 0.1 mol L–1 KCl solution,
Conductivity, k = 1.29 × 10–2 Ω–1 cm–1, Resistance, R = 100 Ω
Cell constant = Conductivity × resistance
= 1.29 × 10–2 Ω–1 cm–1 × 100 Ω = 1.29 cm–1
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For 0.02 mol L–1 solution,
Resistance = 520 Ω, Cell constant = 1.29 cm–1
5 MARK QUESTIONS :
1. The conductivity of sodium chloride at 298K has been determined at different concentrations and the
results are given below: (NCERT Exercise Q.No:2.10)
Concentration / M 0.001 0.010 0.020 0.050 0.100
10-2 x κ / Sm-1 1.237 11.85 23.15 55.53 106.74
Calculate Λ m for all concentrations and draw a plot between Λ m and C1/2. Find the value of Λ om .
Solution :
1 S cm −1
= 1 (Unit conversion factor)
100 S m −1

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2. Conductivity of 0.00241M acetic acid is 7.896 x 10–5 S cm–1.

Calculate its moalr conductivity. If Λ om for acetic acid si 390.5 S cn2 mol–1, what is its dissociation
constant? (Exercise Q.No:2.11)
Solution :
Step I : Calculation of molar conductivity ( Λ cm )
Step II : Calculation of dissociation constant (Ka)

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[Electrolysis, Faraday’s laws]
1 MARK QUESTIONS :
1. What are the products of electrolysis of molten and aqueous sodium chloride?
i) Na and Cl2 ii) H2 and Cl2.
2. Suggest a list of metals that are extracted electrolytically. (Intext Q.No:2.11)

Na, Ca, Mg and Al.
3. Value of standard electrode potential for the oxidation of Cl– ions is more positive than that of water,
even though in the eleotrolysis of aqueous sodium chloride, why is Cl oxidised at anode instead of
water? (Exemplar)
Under the condition of electrolysis of aqueous sodium chloride, oxidation of water at anode requires
over potential. So, Cl– is oxidised at anode instead of water.
4. When acidulated water (dil. H2SO4 solution) is electrolysed, will the pH of the solution be affected?
Justify your answer. (Exemplar)
pH of the solution will not be affected as [H+] remains constant.
At anode : 2H2O → O2 + 4H+ + 4e–
At cathode : 4H+ + 4e– → 2H2
5. Why electrolysis of NaBr and NaI gives Br2 and I2 respectively while that of NaF gives O2 instcad of
F2 ?
Br– and I– ions have higher oxidation potentials than water. Hence, they are more easily oxidised. But F-
ions have lower oxidation potential than H2O. So, H2Ois easily oxidised to give O2 gas.
6. Why does an aqueous solution of NaCl on electrolysis give H2 gas at the cathode and not sodium
metal?
This is because of the fact that standard reduction potential of water is greater thar that of sodium.
2 MARK QUESTIONS :
1. Consider the reaction : (Intext Q.No:2.12)
Cr2 O 72 − + 14H + + 6e − → 2Cr 3+ + 7H 2 O
What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr2O72-?
From the given reaction, 1 mole of Cr2 O 72 − ions require
6F = 6 x 96500 C = 579000 C of electricity for reduction to Cr3+.

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2. How much charge is required for the following reduction : (Exercise Q.No:2.12)
i) 1 mol of Al 3+ to Al ii) 1 mol of Cu2+ to Cu iii) 1 mol of MnO–4 to Mn2+?
Oxidation number of Mn changes from +7 to +2.

∴ Quantity of charge required = 5F = 5 x 96500 C = 482500 C
3. Calculate the time of deposit 1.17g of Ni at cathode when a current of 5A was passed through the
solution of Ni(NO3)2. (CBSE “Bhubaneshwar 2015)
(Molar mass of Ni = 58.5g mol-1, 1F = 96500C mol-1)
4. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would
flow though the wire? (NCERT Intext Q.No:2.10)
A = I x t = 0.5 x 2 x 60 x 60 = 3600C
Charge on 1 electron is 1.602 x 10-19C.
1
3600 C is charge on x3600
1.602 x 10-19
3600
= x 1019 = 2.25 x 10 22 electrons
1.602
5. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 amperes for
20 minutes. What mass of Ni is deposited at the cathode? (Exercise Q.No:2.15)
Quantity of electricity passed = I × t = (5 A) × (20 × 60 s) = 6000 C
The electrode reaction is : Ni2+ + 2e– → Ni
2 x 96500 C deposit Ni = 58.7g
58.7
∴ 6000 C will deposit Ni = x 6000 g = 1.825g
2 x 96500
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6. How much electricity in terms of Faraday is required to produce (Exercise Q.No:2.14)
i) 20.0 g of Ca from molten CaCl2?
ii) 40.0 g of Al from molten Al2O3?
i) Ca2+ + 2e– → Ca
As, 40g of Ca, require electricity = 2F
20
∴ 20g of Ca will require electricity x 2 = 1F
40
ii) Al3+ + 3e– → Al
As, 1 mol of Al, i.e., 27g of Al require electricity = 3F
3
∴ 40g of Al will require electricity = x 40 = 4.44F
27
7. How much electricity is required in coulomb for the oxidation of (Exercise Q.No:14)
i) 1 mol of H2O to O2
ii) 1 mol of FeO to Fe2O3?
i) The electrode reaction for 1 mol of H2O is given as
1
H 2 O → 2H + + O 2 + 2e-
2
∴ Quantity of electricity required = 2F = 2 x 96500C = 193000 C
ii) The electrode reaction is given as
1
2FeO + O 2 → Fe 2 O3
2
i.e., 2Fe2+ → 2Fe3+ + 2e–
∴ For the oxidation 1 mole of FeO, required charge = 1F = 96500C
8. Calculate the time to deposit 1.27 g of copper at cathode when a current of 2 A was passed through
the solution of CuSO4.
(Molar mass of Cu = 63.5 g mol–1, 1 F = 96500 C mol–1)

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9. How many moles of mercury will be produced by electrolysing 1.0 M Hg(NO3)2 solution with a
current of 2.00 A for 3 hours?
Mass of mercury produced at the cathode,
3 MARK QUESTIONS :
1. Aqueous copper sulphate solution and aqueous silver nitrate solution are electrolysed by 1 ampere
current for 10 minutes in separate electrolytic cells. Will the mass of copper and silver deposited on
the cathode be same or different? Explain your answer. (Exemplar)
The mass of copper and silver deposited will be different as it depends on their equivalent weights
according to Faraday’s second law of electrolysis.
Cu2+ + 2e– → Cu
Q = It = 1A x 600s = 600 C
2 x 96487 (2 F) C deposit 63 g of Cu.
63 x 600
600 C will deposit = 0.1959 g Cu.
2 x 96487
Ag+ + 1e– → Ag
1 x 96487 (1 F) C deposit 108 g of Ag.
108 x 600
600 C will deposit = 0.67159 g Ag
96487
2. How will the pH of brine (aq. NaCl solution) be affected when it is electrolysed? (Exemplar)
The pH of solution will rise as NaOH is formed in the electrolytic cell during electrolysis of brine.
NaCl → Na+ + Cl–
H2O → H+ + OH–
1
At cathode : H2O + e– → H2 + OH-
2
1
At anode : Cl– → Cl2 + e–
2
In electrolytic cell, Na+ + OH– → NaOH
1 1
or NaCl + H2O → NaOH + H2 + Cl2
2 2
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3. Three electrolytic cells A, B and C containing solutions of ZnSO4, AgNO3 and CuSO4, respectively
were connected in series. A steady current of 1.5 amperes 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? (Exercise Q.No:2.16)
Ag+ + e– → Ag
108g of Ag is deposited by 96500 C
96500
∴ 1.45 g of Ag will be deposited by x 1.45C = 1295.6C
108
Q 1295.6
t= = = 863.7s
I 1.50
Cu2+ + 2e– → Cu
2 x 96500 C deposit Cu = 63.5g
63.5
∴ Cu deposited by 1295.6C = x 1295.6 = 0.426g
2 x 96500
Zn2+ + 2e– → Zn
2 x 96500 C deposit Zn = 65.3g
65.3
∴ Zn deposited by 1295.6C = x 1295.6 = 0.438g
2 x 96500
4. i) State two advantages of H2—O2 fuel cell over ordinary cell.

ii) Silver is electrodeposited on a metallic vessel of total surface area 500 cm2 by passing a current of
0.5 amp for two hours. Calculate the thickness of silver deposited.
[Given: Density of silver = 10.5 g cm–3, Atomic mass of silver = 108 amu, F = 96,500 C mol–1]
i) Advantages of fuel cell:
a) It is a pollution-free device since no harmful products are formed.
b) Its efficiency is about 75% which is considerably higher than conventional cells.
c) It is a continuous source of energy if the supply of gases is maintained.
ii)
Let the thickness of silver deposited be x cm.

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4 MARK QUESTIONS :
1. a) A current of 1.50 A was passed through an electrolytic cell containing AgNO3 solution with inert
electrodes. The weight of Ag deposited was 1.50 g. How long did the current flow?
b) Write the reactions taking place at the anode and cathode in the above cell.
c) Give reactions taking place at the two electrodes if these are made up of Ag.
a) Ag+ + e– → Ag
Quantity of charge required to deposit 108g of silver = 96500 C
96500
∴ Quantity of charge required to deposit 1.50g of silver = x1.50 = 1340.28C
108
Q
t=
I
1340.28
∴ Time taken = = 893.52s
1.50
b) Inert electrodes
Anode : 2H2O(l) → O2(g) + 4H+(aq) + 4e–
Cathode : Ag+(aq) + e– → Ag(s)
c) Ag electrodes
Anode : Ag(s) → Ag+(aq) + e–
Cathode : Ag+(aq) + e– → Ag(s)
2. Chromium metal can be plated out from an acidic solution containing CrO3 according to the
following equation :
CrO3(aq) + 6H+(aq) + 6e– → Cr(s) + 3H2O
Calculate i) how many grams of chromium will be plated out by 24,000 coulombs and ii) how long
will it take to plate out 1.5g of chromium by using 12.5 A current? (At. mass of Cr = 52).
i) 6 x 96,500 coulomb deposit Cr = 1 mole = 52g
52 x 24000
∴ 24,000 coulomb deposit Cr = g = 2.1554g
6 x 96500
ii) 52g of Cr is deposited by electricity = 6 x 96500 C
6 x 96500
∴ 1.5g require electricity = x 1.5 C = 16071.9C
52
16071.9C
∴ Time for which the current is required to be passed = = 1336s
12.5A
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3. a) State Faraday’s first law of electrolysis. How much charge in terms of Faraday is required for the
reduction of 1 mol of Cu2+ to Cu?
b) Calculate emf of the following cell at 298K :
Mg(s) | Mg2+ (0.1M) || Cu2+ (0.01M) | Cu(s)
[Given E oCell = +2.71 V, 1F = 96500 C mol-1]
a) It states that the amount of chemical reaction which occurs at any electrode during electrolysis by a
current is proportional to the quantity of electricity passed through the electrolyte (solution or melt).
Cu2+ + 2e– → Cu
b)
4. Predict the products of electrolysis in each of the following (Exercise Q.No:2.18)

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.
Solution :
a) Electrolysis of aqueous solution of AgNO3 with silver electrodes:
AgNO3(s) → Ag+(aq) + NO3- (aq)
H2O ⇌ H+ + OH–
At cathode: Since, the reduction potential of Ag+ (+0.80 V) is greater than that of water,
(– 0.83 V), Ag+ will get reduced preferentially and silver metal will get deposited at
the cathode will be deposited as Ag in preference to H+ ions.
Ag+(aq) + e- → Ag(s)

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At anode : Following reactions may take place
1
H2O(l) → O2(g) + 2H+(aq) + 2e–
2
Ag(s) → Ag+(aq) + e-
Among these reactions, the reduction potential of silver is minimum. Therefore, the silver anode will
itself undergo oxidation to form Ag+ ions which will pass into the solution.
b) At cathode: As given in part (i).
At anode: Since the reduction potential of water is less than that of NO3- ions, water will get
preferentially oxidised and oxygen will be evolved.
1
H2O(l) → O2(g) + 2H+(aq) + 2e–
2
c) At cathode :
2H+(aq) + 2e- → H2(g); Eo = 0.00V
2H2O(l) + 2e- → H2(g) + 2OH-(aq); Eo = –0.83V

Since, H+ ions possess a higher reduction potential as compared to that of water, H+ will get
preferentially reduced and H2 gas is obtained at the cathode.
2H+(aq) + 2e- → H2(g)
1
At anode : H2O(l) → O2(g) + 2H+(aq) + 2e–; Eo = +1.23V
2
Since, the reduction potential of H2O is less than that of SO42- ions, water will get preferentially
oxidised and oxygen will be evolved at the cathode.
d) At cathode : 2H2O(l) + 2e- → H2(g) + 2OH-(aq); Eo = –0.83V
Cu2+(aq) + 2e- → Cu(s); Eo = +0.34V

As Eo for Cu2+ is greater than H2O. So, copper metal is deposited at the anode.
1
At anode : H2O(l) → O2(g) + 2H+(aq) + 2e–; Eo = +1.23V
2
2Cl-(aq) → Cl2(g) + 2e-(aq); Eo = +1.36V
Since Eo value of H2O is less than Cl–, water will get preferentially oxidised at anode and O2 gas will
be evolved.

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[Electrochemical cells, Galvanic cells, Nernst Equation, Electro chemical series,
Equilibrium constant (K), ∆G]
1 MARK QUESTIONS :
1. Arrange the following metals in the order in which they displace each other from the solution of their
salts. Al, Cu, Fe, Mg and Zn (NCERT Exercise Q.No:2.1)
Mg, Al, Zn, Fe, Cu. It means that every metal on the left side can displace the next one(s) from it’s salt
solution.
2. Consider a cell given below :

Cu | Cu 2 + || Cl − | Cl 2 , Pt
Write the reactions that occur at anode and cathode. (Exemplar)
Pt is used as cathode
3. What is the necessity to use a salt bridge in a Galvanic cell?

To complete the inner circuit and to maintain the electrical neutrality of the electrolytic solutions of the
half-cells we use a salt bridge in a Galvanic cell.
4. What does the negative sign in the expression E o Zn2+ / Zn = −0.76V mean? (Exemplar)
It means that Zn is more reactive than hydrogen. When zinc electrode will be connected to SHE, Zn
will get oxidized and H+ will get reduced.
5. Write Nernst equation for single electrode potential.
6. Write Nernst equation for the reaction

2Cr + 3Fe2+→ 2Cr3+ + 3Fe

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7. Write the Nernst equation for the cell reaction in the Daniel cell. How will the Ecell be affected when
concentration of Zn2+ ions is increased? (Exemplar)
Ecell decreases when concentration of Zn2+ ions, [Zn2+] increases.
8. Can Eocell or ∆rGo for cell reaction ever be equal to zero? (Exemplar)
No, otherwise the reaction becomes non feasible (E0cell = 0 for concentration cell)
9. Depict the galvanic cell in which the cell reaction is Cu + 2Ag+ → 2Ag + Cu2+. (Exemplar)
Cu | Cu2+ (conc.) || Ag+ (conc.) | Ag
10. Can you store copper sulphate solution in a zinc pot? (NCERT Intext Q.No:2.1)
E o Zn 2+ / Zn = -0.76V, E o Cu 2+ /Cu = 0.34V.
We have to check whether the following reaction takes place or not.
Zn (s ) + CuSO4( aq ) → ZnSO4( aq ) + Cu ( s)
E ocell = ECu
o
2+
/Cu
- E o Zn 2+ / Zn = 0.34V - ( -0.76 V ) = 1.1V
Since Eocell is positive, the reaction takes place and we cannot store CuSO4 solution in a zinc pot.
11. What is electrode potential? (Exemplar)

The electrical potential difference set up between the metal and its ions in the solution is called electrode
potential. It is also defined as the tendency of an electrode to lose or gain electrons when it is in contact
with solution of its own ions.
12. Can absolute eleotrode potential of an electrode be measured? (Exemplar)

No, only the difference in potential between two electrodes can be measured. This is due to the reason
that oxidation or reduction cannot occur alone.
13. Under what condition is Ecell = 0 or ∆rG = 0? (Exemplar)

At the stage of chemical equilibrium in the cell.
14. 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? (Exemplar)
The cell reaction stops completely and no curent flows through the cell.
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15. Which reference electrode is used to measure the electrode potential of other electrodes? (Exemplar)
Standard hydrogen electrode (SHE) is the reference electrode whose electrode potential is taken to be
zero. The electrode potential of other electrodes is measured with respect to it.
16. Define electrochemical series.

The arrangement of single elecrodes in the increasing or decreasing order of their standard reduction
potentials is called electrochemical series.
17. What would happen if no salt bridge were used in an electrochemical cell (like Zn-Cu cell)?
The metal ions (Zn2+) formed by the loss of electons will accumulate in one electrode and the negative
ions (SO 24− ) will accumulate in the other. Thus, the solutions will develop charges and the current will
stop flowing. Moreover, the inner circuit will not be completed.
18. What flows in the internal circuit of a galvanic cell?

Ions.
19. In operation of a galvanic cell, at one of the electrodes oxidation takes place. What is the name of this
electrode and what is its potarity?
Anode is the electrode at which oxidation, i.e., loss of electron takes place. It is -ve terminal.
20. Why is it not possible to measure the single electrode potential?

Oxidation or reduction cannot take place alone. Moreover, electrode potential is a relative tendency and
can be measured with respect to a reference etectrode only.
21. State the factors that influence the value of cel potential of the following cell:
Mg(s) | Mg2+(aq) || Ag+(aq) | Ag(s)
Concentration of Mg2+ and Ag+ ions in the solution and temperature.
22. What is the reference electrode in determining the standard electrode potential?
Normal hydrogen electrode (NHE).
−
23. Write Nernst equation for the general cell reaction aA + bB →
ne
xX + yY .
RT [ X ] [ Y ]
x y
If n moles of electrons are transferred, Nernst equation is E cell = E o

− ln
nF [ A ]a [ B]b
cell
24. What does the negative value of E ocell indicate?

o
Negative Ecell value means ∆rGo will be +ve, and the cell will not work.

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2 MARK QUESTIONS :
1. Write the Nernst equation and the emf of the following cells at 298K : (Exercise Q.No:5(i))
Mg(s) | Mg2+ (0.001 M) || Cu2+ (0.0001 M) | Cu(s)
Given, E oMg 2+ /Mg = −2.37V, E oCu 2+ /Cu = +0.34V
2. Write the Nernst equation and the emf of the following cells at 298 K: (Exercise Q.No:2.5(ii))
Fe(s) | Fe2+ (0.001 M) || H+ (1 M) | H2(g) (1 bar) | Pt(s)
Given, E oFe2+ / Fe = −0.44V .
3. Calculate the equilibrium constant, KC for the reaction :

3Sn4+ + 2Cr → 3Sn2+ + 2Cr3+
Given Eo = 0.885V.

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4. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10. (NCERT
Intext Q.No:2.4)
For hydrogen electrode,
1
H + + e- → H2
2
From Nernst equation,
0.0591 1
E H + /H = E oH + /H - log +
2 2
n  H 
0.0591 1
=0- log -10
1 10
= 0.0591 x 10 = –0.591V
5. How would you determine the standard electrode potential of the system Mg2+ / Mg? (Intext
Q.No:2.1)
Eo value of Mg2+ / Mg electrode is determined by setting up an electrochemical cell. For this purpose, a
Mg electrode is dipped in 1M MgSO4 solution, which acts as one half cell i.e., oxidation half-cell.
In the same way, the standard hydrogen electrode acts as the other half-cell i.e., reduction half cell. The
deflection of voltmeter placed in the cell circuit is towards the Mg electrode which indicates the
direction of flow of current.
The cell may be represented as :
Mg | Mg2+(1M) || H+(M) | H2(1 atm), Pt
The reading as given by voltmeter gives E ocell
E ocell = E oH+ /1/2H − E oMg 2+ /Mg = 0 − E oMg 2+ /Mg

( 2 ) ( ) ( )

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6. Given the standard electrode potentials, (Exercise Q.No:2)
K+/ K = -2.93 V, Ag+ / Ag = 0.80 V Hg2+ / Hg = 0.79V,
Mg2+ / Mg = -2.37V, Cr3+ / Cr = - 0.74 V
Arrange these metals in their increasing order of reducing power.
Metal which has lower reduction potential (more negative Eo value) has greater reducing capacity
because it itself gets oxidised more easily.
7. Depict the galvanic cell in which the reaction, Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s) takes place.
Further show: (Exercise Q.No:2.3)
i) Which of the electrode is negatively charged?
ii) The carriers of the current in the cell.
iii) Individual reaction at each electrode.
The galvanic cell for the reaction is represented as
Zn(s) | 2Ag+(aq) || Zn2+(aq) + 2Ag(s)
i) Zinc electrode (anode) is negatively charged.
ii) Electrons and ions
iii) Anode Zn(s) 

Oxidation
→ Zn 2+ ( aq ) + 2e −
Cathode 2Ag ( aq ) + 2e− 

Reduction
→ 2Ag ( s )
1
8. Consider a cell given below Cu | Cu2+ || Cl–| Cl2, Pt. Write the reactions that occur at anode and
2
cathode. (Exemplar)
At anode Cu → Cu2+ 2e–
At cathode Cl2 + 2e– → 2Cl–

Copper is getting oxidised at anode. Cl2 is getting reduced at cathode.

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3 MARK QUESTIONS :
1. Calculate the standard cell potentials of galvanic cells in which the following reactions take place :
2Cr(s) + 3Cd2+(aq) → 2Cr3+ + (aq) + 3Cd(s) (NCERT Exercise Q.No:2.4(i))
Given, E oCr3+ /Cr = −0.74V, E Cd
o
2+
/Cd
= −0.40V,
Also calculate ∆rGo and equilibrium constants of the reactions.
2. Calculate e.m.f and ∆G for the following cell at 298 K :

Mg(s) | Mg2+ (0.01M) || Ag+ (0.0001M) | Ag(S)
Given : E oMg2+ /Mg = −2.37V, E oAg+ /Ag = +0.80V
( ) ( )

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3. Calculate the emf of the cell in which the following reaction takes place: (NCERT Intext Q.No:2.5)
Ni(s) + 2Ag+(0.002M) → Ni2+ (0.160M) + 2Ag(s) Given that Eocell = 1.05V
Ni( s ) → Ni (2+aq ) + 2e-
2Ag +( aq ) + 2e - → 2Ag (s )
Ni( s ) + 2Ag + ( aq ) → Ni(2+aq ) + 2Ag (s )
 Ni 2+ 
log 
o 0.0591
E cell = E cell - 2
2  Ag + 
0.0591 0.16
= 1.05 - log
( 0.002 )
2
2
0.0591 0.16
= 1.05 - log
2 4 x 10-6
0.0591 x 4.602
= 1.05 -
2
= 1.05 – 0.1358 = 0.9142
4. The cell in which the following reaction occurs : 2Fe3+(aq) + 2l–(aq) → 2Fe2+(aq) + I2(s) has Eocell =
0.236V at 298K. Calculate the standard Gibb’s energy and the equilibrium constant of the cell
reaction. (NCERT Intext Q.No:2.6)
2Fe3+ + 2e– → 2Fe2+
2I– → I2 + 2e–
2Fe3+ + 2I– → I2 + 2Fe2+; Eocell = 0.236V
∆Go = –nEoF = –2 x 0.236 x 96500
= –45548 J mol–1 = –45.54kJ mol–1
∆Go = –2.303 RT log K
∆G o
logK = -
2.303RT
- ( -45548 )
= = 7.98
2.303 x 8.314 x 298
K = 9.61 x 107

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5. Calculate ∆rGo and log KC for the following reaction at 298K :
2Cr(s) + 3Fe2+(aq) → 2Cr3+(aq) + 3Fe(s) Given : Eocell = 0.30V
Here, n = 6, Eocell = 0.30V

n
Substituting the values in expression, log KC = Eocell, we get
0.059
6. i) Represent the cell in which the following reaction takes place:

2Al (s) + 3Ni2+ (0.1M) → 2Al3+ (0.01M) + 3Ni(s)
Calculate the emf if Eocell = 1.41 V.
ii) How does molar conductivity vary with increase in concentration for strong electrolyte and weak
electrolyte? How can you obtain limiting molar conductivity ( Λ om ) for weak electrolyte?
i) 2Al (s) + 3Ni2+ (0.1M) → 2Al3+ (0.01M) + 3Ni(s), n = 6
Cell representation : Al(s) | Al3+ (0.001M) || Ni2+ (0.1M) | Ni(s)
Here, n = 6, Εocell = 1.41V, [Ni2+] = 0.1M, [Al3+] = 1 x 10-2 M
ii) With increase in concentration, the greater interionic attraction retard the motion of the ions and
therefore, the molar conductivity falls for both with increasing concentration. The limiting molar
conductivity ( Λ om ) for weak electrolyte can be calculated by using Kohlrausch’s law.
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7. In the button cell widely used in watches and other devices the following reaction takes place:
Zn(s) + Ag2O(s) + H2O(l) → Zn2+(aq) + 2Ag(s) + 2OH–(aq) (Exercise Q.No:2.6)
Determine ∆rGo and Eo for the reaction.
Given : E o 2+ = 0.76V and E o + + 0.34V 
 Zn / Zn Ag / Ag 
Solution :
[Given, Zn → Zn2+ + 2e-, Eo = –0.76V
Ag2O + H2O + 2e– → 2Ag + 2OH–; Eo = (0.80 – 0.45) V]
In the given electrochemical cell, zinc is oxidised and silver ions are reduced.
8. What is the relationship between Gibbs free energy of the cell reaction in a galvanic cell and the emf
of the cell? When will the maximum work be obtained from a galvanic cell?
If concentration of all reacting species is unity, then Ecell = Eocell.
and ∆ r G o = −nFE cell
o
Where ∆rGo is standard Gibbs energy of the reaction.

E ocell = emf of the cell
nF = charge passed
If we want to obtain maximum work from a galvanic cell then charge has to be passed reversibly.
The reversibly work done by a galvanic cell is equal to decrease in its Gibbs energy.
∆rG = – nFEcell
As Ecell is an intensive parameter but ∆rG is an extensive thermodynamic property and the value
depends on n.
For reaction, Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) in a galvanic cell.
∆rG = – 2FEcell
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9. A zinc rod is dipped in 0.1M solution of ZnSO4. The salt is 95% dissociated at this dilution at 298K.
(
Calculate the electrode potential E oZn 2+ / zn = −0.76V . )
The electrode reaction written as reduction reaction is
Zn2+ + 2e– → Zn (n = 2)
Applying Nernst equation, we get
0.0591 1
E Zn 2+ / Zn = E oZn 2+ / Zn − log
2  Zn 2 + 
As 0.1 M ZnSO4 solution is 95% dissociated, this means that in the solution,
95
 Zn 2 +  = x 0.1M = 0.095M
100
0.0591 1
∴ E Zn 2+ / Zn = −0.76 − log
2 0.095
= –0.76 – 0.02955 (log 1000 – log 95)
= –0.76 – 0.02955 (3 – 1.9777) = –0.76 – 0.03021
= –0.79021 V
10. The emf of a cell corresponding to the reaction.

Zn(s) + 2H+(aq) → Zn2+ (0.1M) + H2 (g, 1 atm) is 0.28 volt at 25oC.
Write the half-cell reactions and calculate the pH of the solution at the hydrogen electrode.
E oZn 2+ / Zn = −0.76V, E oH+ /H = 0V
2
Solution : Half-cell reactions :

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11. Estimate the minimum potential difference needed to reduce Al2O3 at 500oC. The free energy change
for the decomposition reaction.
Solution :
∴ Minimum potential difference needed to reduce Al2O3 is +2.487 V.
12. The electrochemical cell given alongside converts the chemical energy released during the redox
reaction Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) to electrical energy. It gives an electrical potential of
1.1V when concentration Zn2+ and Cu2+ ions is unity. State the direction of flow of current and also
specify whether zinc and copper are deposited or dissolved at their respective electrodes when:
i) an external opposite potential of less than 1.1 V is applied.
ii) an external potential of 1.1 V is applied.
iii) an external potential of greater than 1.1 V is applied.

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i) Reaction continues to take place.
Electlons flow from Zn electrode to copper electrode, hence curent flows from cu to zn. Zn dissolves
and copper deposits at their respective electrodes.
ii) The reaction stops and no current flows.
A state of equitibrium is achieved and no change is observed at zinc and copper electrodes.
iii) Reaction takes place in opposite directions.
Electrons flow from copper electrode to zinc electrode and hence current flows from Zn to Cu.
Zinc deposits and copper dissolves at their respective electrodes. The cell functions as an
electrolytic cell.
13. a) Calculate the standard free energy change for the following reaction at 25oC.
Au(s) + Ca2+(1M) → Au3+ (1 M) + Ca(s)
E oAu 3+ / Au = +1.50V, E Ca
o
2+
/Ca
= −2.87V
Predict whether the reaction will be spontaneous or not at 25oC. Which of the above two half cells
will act as an oxidising agent and which one will be a reducing agent?
b) Tarnished silver contains Ag2S. Can this tarnish be removed by placing tarnished silver ware in
an aluminium pan containing an inert electrolytic solution such as NaCl? The standard electrode
potential for half reaction:
Ag2S(s) + 2e– → 2Ag(s) + S2– is –0.71 V
and for Al3+ + 3e– → 2Αl(s) is –1.66 V
Solution :
a) E ocell = E Ca
o
2+
/Ca
− E oAu 3+ /Au = (–2.87 V) – (1.50V) = –4.37 V
∆ r G cell
o
= –6 x 96500 x (–4.37 V) = +2530.230 kJ / mol
Since ∆rGo is positive, therefore, reaction is non-spontaneous.

Au3+/Au half cell will be an oxidising agent while Ca2+/Ca half cell will be a reducing agent.
b) E ocell for reaction of tarnished silver ware with aluminium pan is
(–0.71 V) – (–1.66V) i.e., + 0.95V
Tranished silver ware, therefore, can be cleaned by placing it in an aluminium pan as E ocell is
positive.

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4 MARK QUESTIONS :
1. One half-cell in a voltaic cell is constructed from a silver wire dipped in silver nitrate solution of
unknown concentration. The other half-cell consists of a zinc electrode in a 0.10 M solution of
Zn(NO3)2. A voltage of 1.48 V is measured for this cell. Use this information to calculate the
concentration of silver ions in the solution.
(Given E oZn 2+ / Zn = -0.763V, E oAg + / Ag = +0.80V )
Electrochemical cell
We know that,
2. Read the passage given below and answer the following questions
The standard electrode potentials are very important and we can extract a lot of useful information from
them. If the standard electrode potential of an electrode is greater than zero then its reduced form is
more stable compared to hydrogen gas. Similarly, if the standard electrode potential is negative then
hydrogen gas is more stable than the reduced form of the species. It can be seen that the standard
electrode potential for fluorine is the highest in the Table indicating that fluorine gas (F2) has the
maximum tendency to get reduced to fluoride (F-) and therefore fluorine gas is the strongest oxidizing
agent and fluoride ion is the weaker reducing agent. Lithium has the lowest electrode potential
indicating that lithium metal is the most powerful reducing agent in an aqueous solution.

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i) A negative E0 means that
1. the redox couple is a stronger reducing agent.
2. the redox couple is a stronger oxidizing agent.
3. the redox couple is a weak reducing agent.
4. the reaction is spontaneous in the forward direction.
Ans : (1)
ii) Standard Electrode Potential is _________
1. the reduction potential of a molecule under specific and standard conditions.
2. extensive property.
3. measured by calorimeter.
4. oxidation potential.
Ans : (1)
iii) The standard hydrogen electrode can be represented as
1. Pt (s) / Pt+2 (aq) / H2 (g) / H+ (aq.)
2. Pt (s) / H2 (g, 1 bar) / H+ (aq, 1M)
3. Pt (s) / H2 (g, 2 bar) / H+ (aq, 1M)
4. Pt (s) / H2 (g, 4 bar) / H+ (aq, 2M)
Ans : (2)
iv) E0 Mg+2/Mg = -2.36 V, E0 Ag+/Ag = 0.80 V. The E0 cell is _______
1) -3.16 V 2) -1.56 V 3) 2.3 V 4) 3.16
Ans : (4) E0cell = E0Ag+/Ag – E0Mg2+/Mg = 0.8 – (– 2.36) = 3.16
3. Read the passage given below and answer the following questions
A Galvanic cell is made up of two electrodes anode and cathode, i.e., two half cells. One of these
electrodes must have a higher electrode potential (higher tendency to lose electrons) than the other
electrode. As a result of this potential difference, the electrons flow from an electrode at a higher
potential to the electrode at a lower potential. There is a difference between electromotive force and
potential difference.
i) In a Galvanic cell ,the potential difference and emf are respectively measured by
a) Ammeter and calorimeter b) Ammeter and Voltmeter
c) Voltmeter and potentiometer d) Potentiometer and Voltmeter
Ans : (d)

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ii) In a galvanic cell
a) the flow of electron is from anode (negative zinc electrode) towards cathode (positive copper
electrode)
b) the flow of electron is from cathode (positive copper electrode) towards anode (negative zinc
electrode)
c) the electric current flows from anode to cathode .
d) the electrons are transferred from the oxidizing agent to the reducing agent.
Ans : (a)
iii) In a Galvanic cell
a) According to IUPAC convention, electrode potentials are expressed as standard oxidation
potential
b) standard electrode potential can be measured experimentally.
c) Oxidation potential is the tendency to release electrons.
d) the electrode potential values represent the standard reduction potential ,standard oxidation
potential will have the same values but with opposite sign
Ans : (d)
iv) Which of the following is not true about the electrode potential ?
a) Electrode potential depends on the nature of the metal.
b) Electrode potential is an extensive property.
c) Electrode potential depends on the concentration of the ions in solution.
d) Electrode potential depends on the temperature.
Ans : (b)
4. i) Calculate Eocell for the following reaction at 298 K:

2Al(s) + 3Cu2+ (0.01M) → 2Al3+ (0.01M) + 3Cu(s)
Given: Ecell = 1.98 V
ii) Using the Eo values of A and B, predict which is better for coating the surface of iron
 E Fe
o
2+
/ Fe
= -0.44V  to prevent corrosion and why?
Given :  E Ao 2+ / A = -2.37V, E Bo 2+ / B = -0.14V 
i)
Here, n = 6, Ecell = 1.98 V, [Al3+] = 1 × 10–2 M, [Cu2+] = 1 × 10–2 M

Substituting these values in the Nernst equation for above electrochemical change,
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ii) A, as its standard reduction potential is less than B, therefore, it will undergo oxidation more easily
than B.
5. Calculate the standard cell potentials of galvanic cell in which the following reactions take place:
Fe2+ (aq) + Ag+(aq) → Fe3+(aq) + Ag(s) (Exercise Q.No:2.4(ii))
Calculate the ∆rGo and equilibrium constant for the reactions.
Given E oAg+ /Ag = 0.80V; E oFe3+ /Fe2+ = 0.77V

( ) ( )

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6. Write the Nernst equation and emf of the following cells at 298K: (Exercise Q.No:2.5(iii) & (iv))
i) Sn(s) |Sn2+ (0.050M) || H+(0.020 M| H2(g) (1 bar) |Pt(s)
ii) Pt(s) | Br2(l) | Br–(0.010M) || H+(0.030M) |H2(g) (1 bar) | Pt(s)
Given :
i) Cell Equation : Sn(s) + 2H+(aq) → Sn2+(aq) + H2(g) (n = 2)
ii) Cell Equation : 2Br–(l) + 2H+(aq) → Br2(l) + H2(g)

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7. PConsider the following diagram and answer the questions given below:
i) Cell ‘A’ has Ecell = 2V and cell ‘B’ has Ecell = 1.1V. Which of the two cell ‘A’ or ‘B’ will act as an
electrolytic cell which electrode reactions will occur in this cell?
ii) If cell ‘A’ has Ecell = 0.5V and cell ‘B’ has Ecell = 1.1V then that will be the reactions at anode and
cathode?
Solution:
i) Cell ‘B’ will act as electrolytic cell due to its lesser value of emf. The electrode reactions will be
At cathode Zn2+ + 2e– → Zn
At anode Cu → Cu2+ + 2e–
ii) If cell ‘B’ has higher emf, it acts as galvanic cell. Now it will push electrons into cell ‘A’. In this
case the reactions will be:
Zn → Zn2+ + 2e– (At anode)
Cu2+ 2e– → Cu (At cathode)
8. One half-cell in a voltaic cell is constructed from a silver wire dipped in silver nitrate solution of
unknown concentration. The other half-cell consists of a zinc electrode in a 0.10M solution of
Zn(NO3)2. A voltage of 1.48V is measured for this cell. Use this information to calculate the
concentration of silver ions in the solution. (CBSE (F) 2010)
( Given E o
Zn 2+ / Zn
= −0.763V, E oAg+ /Ag = +0.80V )
Solution : Electrochemical cell

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5 MARK QUESTIONS :
1. i) What type of a battery is lead storage battery? Write the anode and cathode reactions and the
overall cell reaction occurring in the operation of a lead storage battery.
ii) Calculate the potential for half-cell containing
0.10M K2Cr2O7 (aq), 0.20 M Cr3+(aq) and 1.0 × 10–4 M H+(aq). The half cell reaction is
Cr2O7 2–(aq) + 14H+(aq) + 6e– → 2Cr3+(aq) + 7H2O(l)
and the standard electrode potential is given as Eo = 1.33V.
i) Lead storage battery is secondary cell. It consists of a lead anode and grid of lead packed with lead
oxide (PbO2) as cathode. A 38% solution of H2SO4 is used as electrolyte.
The cell reactions are
Anode : Pb(s) + SO -24 → PbSO 4 + 2e -
Cathode : PbO 2 + SO-24 + 4 H +1 + 2e - → PbSO 4 + 2H 2 O
i.e., overall cell reaction consisting of cathode and anode reaction is

Pb (s) + PbO 2(s) + 2H 2SO 4(aq) → 2PbSO 4(s) + 2H 2 O ( l )
ii) For half cell reaction
Here, Eo = 1.33 V, n = 6, [Cr3+] = 0.2 M

[Cr2O72–] = 0.1 M, [H+] = 1 × 10–4 M
Substituting these values in the given expression, we get

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2. Using the standard electrode potential values; predict if the reaction between the following is feasible:
(Exercise Q.No:17)
i) Fe3+(aq) and I–(aq)
ii) Ag+(aq) and Cu(s)
iii) Fe3+(aq) and Br–(aq)
iv) Ag(s) and Fe3+(aq)
v) Br2(aq) and Fe2+(aq)
Given standard electrode potentials
Solution :
A reaction is feasible, if its E ocell value is positive.

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3. Consider the following diagram and answer the questions (i) to (vi) given below.
i) Redraw the diagram to show the direction of electron flow.
ii) Is silver plate the anode or cathode?
iii) What will happen if salt bridge is removed?
iv) When will the cell stop functioning?
v) How will concentration of Zn2+ ions and Ag+ ions be affected when the cell functions?
vi) How will the concentration of Zn2+ ions and Ag+ ions be affected after the cell becomes ‘dead'?
Solution :
i) Electrons move from Zn to Ag as Eo is more negative for Zn so Zn undergoes oxidation and Ag+
undergoes reduction.
ii) Ag is the cathode as it is the site of reduction.
iii) Cell will stop functioning because cell potential drops to zero.
iv) When Ecell = 0
v) Concentration of Zn2+ ions will increase and concentration of Ag+ ions will decreases because Zn is
converted into Zn2+ and Ag+ is convered into Ag.
vi) When Ecell = 0 equilibrium is reached and concentration of Zn2+ ions and Ag+ will not change.

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[Batteries, corrosion]
1 MARK QUESTIONS :
1. What are secondary cells?
Secondary cells are those cells which are rechargeable, i.e., the products can be changed back to
reactants.
2. Suggest two materials other than hydrogen that can be used as fuels in fuel cells.
Methyl alcohol and methane.
3. Unlike dry cell, the mercury cell has a constant cell potential throughout its useful life. Why?
(Exemplar)
Ions are not involved in the overall cell reaction of mercury cells.
4. Write the chemistry of recharging the lead storage battery, highlighting all the materials that are
involved during recharging. (Intext Q.No:7)
Chemical reactions while recharging : 2PbSO4 + 2H2O → PbO2 + Pb + 2H2SO4 Electricity is passed
through the electrolyte PbSO4 which is converted into PbO2 and Pb.
5. Why does a dry cell become dead after a long time even if it has not been used?
Even though not in use, a dry cell becomes dead after some time because the acidic NH4C1 corrodes the
zinc container.
6. What is the role of ZnCl2 in a dry cell?

ZnCl2 combines with the NH3 produced to form the complex salt [Zn(NH3)2Cl2] otherwise the pressure
developed due to NH3 would crack the seal of the cell.
7. Which type of a metal can be used in cathodic protection of iron against rusting?
A metal which is more electropositive than iron such as Al, Zn, Mg can be used in cathodic protection of
iron against rusting.
8. What is the overall electrochemical reaction taking place in rusting?

2Fe(s) + O2(g) + 4H+ (aq) → 2Fe2+(aq) + 2H2O(l)

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9. Write the chemical formula of rust.
Fe2O3. xH2O
10. What is cathodic protection?

A process in which a metal is connected with a more reactive metal which acts as anode and the metal to
be protected acts as a cathode is known as cathodic protection.
11. Rusting of iron is quicker in saline water than in ordinary water. Give reason.
In saline water, the presence of Na+ and Cl– ions increases the conductance of the solution in contact
with the metal surface. This accelerates the formation of Fe2+ ion and hence that of rust, Fe2O3.xH2O.
12. What is galvanization?

The process of coating zinc over iron is called galvanization.
13. Three iron sheets have been coated separately with three metals A, B and C whose standard electrode
potentials are given below.
Metal A B C Iron
Eo -0.46V -0.66V -0.20V -0.44V
Identify in which case rusting will take place faster when coating is damaged.
As iron (–0.44V) has lower standard reduction potential than C (–0.20V) only therefore when coating is
broken, rusting will take place faster.
2 MARK QUESTIONS :
1. Write the anode and cathode reactions occurring in a commonly used mercury cell. How is the
overall reaction represented? (CBSE (F) 2010)
Chemical reactions of mercury cell

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2. Write the cell reaction of a lead storage battery when it is discharged. How does the density of the
electrolyte change when the battery is discharged? (Exemplar)
Pb + PbO2 + 2H2SO4 → 2PbSO4 + 2H2O
Density of electrolyte decreases as water is formed and sulphuric acid is consumed as the reactant during
discharge of the battery.
3. For the given cells:

Lead storage cell, Mercury cell, Fuel cell and Dry cell
Answer the following:
1. Which cell is used in hearing aids?
2. Which cell was used in Apollo space programme?
iii) Which cell is used in automobiles and inverters?
iv) Which cell does not have long life?
i) Mercury cell ii) Fuel cell iii) Lead storage cell iv) Dry cell
4. Write the name of the cell which is generally used in hearing aids. Write the reactions taking place at
the anode and the cathode of this cell.
Mercury cell
5. What advantage do the fuel cells have over primary and secondary batteries? (Exemplar)
Primary batteries contain a limited amount of reactants and are discharged when the reactarlts have been
consumed, Secondary batteries can be re.harged but it take a long time. Fuel cell run continuously as
long as the reactants are supplied to it and products are removed coutinuously.
6. Write electrode reactions taking place in i) Ni – Cd cell, ii) Lead Acid Accumulator.
i) Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e–
NiO2(s) + 2H2O + 2e– → Ni(OH)2(s) + 2OH–(aq)
ii) Pb → Pb2+ + 2e– (at anode)
PbO 2 + SO 24− + 4H + + 2e − → PbSO 4 + 2H 2O (at cathode)

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7. Account for the following:
i) Alkaline medium inhibits the rusting of iron.
ii) Iron does not rust even ifthe zinc coating is broken in a galvanized iron pipe.
Solution :
i) The alkalinity of the solution prevents the availability of H+ ions.
ii) Zinc has lower reduction potential than iron- Therefore, zinc coating acts as anode and the exposed
iron portions act as cathode. If zinc coating is broken, zinc still undergoes oxidation, protecting iron
from rusting. No attack occurs on iron till all the zinc is corroded.
3 MARK QUESTIONS :
1. Explain how rusting of iron is envisaged as setting up of an electrochemical cell. (Intext Q.No:2.15)
The following reactions take place at the surface of iron metal which acts as an electrochemical cell.
Oxidation : Fe(s ) → Fe(2+aq ) + 2e-
Reduction : O 2( g ) + 4H (+aq ) + 4e- → 2H 2 O( l )
Atmospheric oxidation : 2Fe(2+aq ) + 2H 2 O( l ) +1 / 2O 2( g ) → Fe 2O3( s) + 4H (+aq )

The water layer present on the surface of iron dissolves acidic oxides of air like CO2 to form acids which
dissociate to give H+ ions. Fe starts losing electrons in presence of H+ ions.
H 2 O + CO 2 → H 2 CO3 ⇌ 2H + + CO 32-
2. The chemistry of corrosion of iron is essentially an electrochemical phenomenon. Explain the

reactions occurring during the corrosion of iron in the atmosphere.
According to electrochemical theory of rusting, the impure iron surface behaves like small
electrochemical cell in the presence of water containing dissolved oxygen or carbon dioxide. In this cell
pure iron acts as anode and impure iron surface acts as cathode. Moisture having dissolved CO2 or O2
acts as an electrolyte.
The reactions are given below.
The Fe2+ ions are further oxidised by atmospheric oxygen to Fe3+ ions, which comes out in the form of
hydrated ferric oxide (rust).

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4 MARK QUESTIONS :
1. Shweta, a student of science, went with her grandfather to buy a battery for their inverter and camera.
The shopkeeper showed them two types of batteries, one a lead storage battery and other a nickel-
cadmium storage battery. The latter was more expensive but lighter in weight. Shweta insisted on
purchasing the costlier nickel-cadmium battery.
i) In your opinion, why did Shweta insist for nickel-cadmium battery? Give reasons.
ii) What type of cell is nickel-cadmium cell?
iii) Write the values associated with the above decision.
iv) Give the equation for overall reaction that takes place in a nickel-cadmium cell during discharge.
Solution :
i) Lead has toxic effects on human beings and the environment. Lead batteries thus lead to long-term
harms. Therefore, it is wise to opt for nickel-cadmium batteries for long-term gains.
ii) Secondary cell.
iii) Values : Scientific knowledge, environmental concern.
iv) Cd(s) + 2Ni(OH)3(s) → CdO(s) + 2Ni(OH)2(s) + H2O(l)
2. Anil and his neighbour Sunil have got their garden fenced with iron rods. Anil saw the next day that
Sunil was painting the iron fence. Sunil suggested Anil to do the same to increase the longevity of the
iron rods by preventing corrosion. Anil argues that it is a waste of time and his iron rods are quite
strong.
After reading the passage, answer the following questions:
i) Whose opinion is correct according to you? What values are promoted here?
ii) Why do car owners living near the sea wash their cars regularly?
iii) Are there any other ways to prevent corrosion other than painting?
iv) Give the equation for overall reaction that occurs during rusting.
i) Sunil is correct because painting cuts off the contact of air and moisture with iron. Both air and
moisture are required for corrosion to occur.
Values : Knowledge / Preservation.
ii) Salt speeds up the rusting of iron. The metal in car would rust faster by the deposition of salt on
them if not washed regularly.
iii) Other methods are : oiling / greasing, covering with plastic, galvanising.
iv) 2Fe(s) + O2(g) + 4H+(aq) → 2Fe2+(aq) + 2H2O(l), E ocell = 1.67V
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3. In a research article Joseph came to know that things made of iron can be protected by sacrificial
protection method. After going through in detail he came to know that in this process iron will be
replaced by some other substance to protect it from rusting.
Now answer the following questions.
i) Explain the sacrificial process in detail,
ii) Explain galvanization process.
iii) Which method can be used to prevent the rusting of submarines and base line of oil refineries?
iv) Write the values associated with Joseph's nature.
Solution :
i) Coating of surface of iron with more reactive metal than iron to prevent rusting is known as
sacrificial process.
ii) The process of coating of iron surface by zinc is called galvanization. Zinc will lose electron and will
undergo oxidation in preference to iron to protect it from rusting.
iii) Cathodic protection method is used to prevent rusting of submarines and base line of oil refineries.
iv) Curiosity and Scientific knowledge are the values associated with Joseph's nature.
4. Gaurav went to purchase Lead storage battery for his car. He visited to a nearest retail battery shop.
He asked about some details regarding internal volume, number of plates of lead and lead oxide, and
the efficiency of battery.
Now answer the following questions.
i) Why does Gaurav need such details?
ii) What is a secondary cell?
iii) What are the characteristics of a useful battery?
iv) What values are associated with Gaurav?
Solution :
i) As a customer he wants to know about working efficiency of battery and its constitution. This way
he can choose from the options available as per his requirement.
ii) A cell which can be recharged by passing electic curent through it and hence can be used over and
again is called a secondary cell, e.g., nickel-cadmium storage cell.
iii) It shoutd be light in weight, compact in size, long lasting when not in use and should not vary
appreciably during its use.
iv) Gaurav have scientific knowledge and is an aware customer.

138
HALOALKANES AND HALOARENES

[CLASSIFICATION, NOMENCLATURE, ISOMERISM, NATURE OF C–X BOND]
1 MARK QUESTIONS :
1. Give one chemical test to distinguish between C2H5Br and C6H5Br.
Hydrolysis of C2H5Br with aqueous KOH followed by acidification with dil HNO3 and
subsequent treatment with AgNO3 gives light yellow ppt of AgBr where as C6H5Br does not
give this test.
2. Which of the following is an example of vic-dihalide?

vic-dihalides are those halides in which two halogen atoms are present on the two adjacent
carbon atoms.
In 1, 2-dichloroethane, the two chlorine atoms are attached to two adjacent carbon atoms.
3. What should be the correct IUPAC name for diethylbromomethane?

Structure of the diethylbromomethane is given below
So, the IUPAC name is 3-bromopentane.
4. The common and IUPAC names of the compound respectively are
Common name: sym-tribromobenzene

IUPAC name: 1, 3, 5-tribromobenzene

139
5. Write the structure of 3-bromo-2-methylprop-1-ene.

The structure of 3-bromo-2-methylprop-1-ene is BrCH 2 − C = CH 2
|
CH 3
6. Out of , which is an example of allylic halide?
In allylic halides, the halogen is bonded to the sp3-hybridised carbon atom next to a carbon-
carbon double bond. Thus,
is an allylic halide.
7. Give the IUPAC name of the following compound.
CH 2 = C − CH 2 Br
| (or)
CH 3
Solution:
1 2 3
C H 2 = C− C H 2 Br IUPAC Name : 3-bromo-2-methylpropene
|
CH 3
8. Write the IUPAC name of the following compound.
Solution :
IUPAC Name of the given compound is 1, 4-dichloro-2-methylbenzene

140
9. Which of the carbon atoms present in the molecule given below are asymmetric?
Solution :
If a carbon atom satisfies all of its four valencies with four different groups then it is termed as
asymmetric / chiral carbon. In the given compound, C – 2 and C – 3 are bonded to four different
groups, so these are asymmetric.
2 MARK QUESTIONS :
1. Arrange each set of compounds in the order of increasing boiling points.
i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
ii) 1 – Chloropropane, Isopropyl chloride, 1- Chlorobutane.
Solution :
i) Chloromethane < Bromomethane < Dibromo methane < Bromoform
∴ Boiling point increases with increase in molecular mass.
ii) Isopropyl Chloride < 1- Chloropropane < 1 – Cholorobutane.
Isopropyl chloride being branched has lower boiling point than 1 – Chloropropane.
2. Give the structural formula and IUPAC name of the following compounds:
i) BHC
ii) DDT
Solution :
i) BHC = Benzene hexachloride
Cl
Cl Cl C6H6Cl6
Cl Cl
Cl
IUPAC = 1, 2, 3, 4, 5, 6- Hexachloro cyclohexane.
ii) DDT = P, P1- dichlorodiphenyl trichloroethane
Cl
Cl CH CCl3
IUPAC name: 2, 2 – Bis (4 – chlorophenyl) - 1, 1, 1 – tricholoroethane

141
3. Arrange each set of compounds in order of increasing boiling points.
i) Bromomethane, bromoform, chloromethane, dibromomethane.

ii) 1-Chloropropane, isopropyl chloride, 1-chlorobutane
The boiling points of organic compounds depend on the strength of the intermolecular forces in
them. These forces are: (a) van der Waals forces and (b) dipole-dipole interactions
These forces are dependent on the (i) molecular mass and (ii) surface area of the molecules
i) As the molecular mass of the compound increases, the boiling point also increases.
Therefore the correct order is chloromethane < bromomethane < dibromomethane <
bromoform
ii) Amongst molecules with same mass, it is the size of the molecule that determines the boiling
point. Branched compounds are more compact and therefore have less surface area as
compared to their straight chain counterparts and therefore lower boiling point. The order of
boiling point is
iso-propyl chloride < 1-chloropropane < 1-chlorobutane
4. Write the structures of the following compounds:
i) 1,4-Dibromobut-2-ene
ii) 1-Bromo-4-sec-butyl-2-methylbenzene
Solution :
i)
ii)

142
5. Write the structures of the following organic halogen compounds.

i) 1-Bromo-4-sec-butyl-2-methylbenzene
ii) 1,4-Dibromobut-2-ene
Structures of the given compounds are:
i)
ii)
6. Write the isomers of the compound having formula C4H9Br.

The possible isomers of C4H9Br are
i) H3C – CH2 – CH2 – CH2 – Br
ii) H3C – CH2 – CH(Br) – CH3
iii)
iv)
7. What are ambident nucleophiles? Explain with an example.

Ambident nucleophiles are nucleophiles that are capable of attacking the substrate (alkyl halide)
through two different atoms.
It so happens due to the presence of two nucleophilic centres which arise from the contributing
(resonance) structures that are possible for the ion. E.g., In NO2- ion, there is a lone pair of
electrons on N and therefore makes it nucleophilic while oxygen by virtue of the negative charge
acts as a nucleophile. Thus, NO2- can attack via O or N atom thereby making it ambidentate.
RX + Ag − O − N = O → R − NO2
nitroalkane
RX + KNO2 → R − O − N = O
alkyl nitrite

143
8. p-Dichlorobenzene has higher m.p. than those of o- and m-isomers. Discuss.

The para-isomers have high melting points as compared to their ortho and meta isomers due to
symmetry of para-isomers that fits into crystal lattice better than ortho and para isomers.
9. Write the structures of different dihalogen derivatives propane.

The structures of different dihalogen derivatives of propane are :
1 2 3
i) Br − C H 2 − C H 2 − C H 2 − Br
1, 3-dibromopropane (I)
1 2 3
ii) Br − C H 2 − C H − C H 3
|
Br
1, 2-dibromopropane (II)
3 2 1
iii) C H 3 − C H 2 − C H − Br
|
Br
1, 1-dibromopropane (III)
Br
|
3 2 1
iv) C H 3 − C− C H 3
|
Br
2, 2-dibromopropane
10. Arrange the following compounds in the increasing order of their densities.
Solution:
< < <

144
3 MARK QUESTIONS :
1. Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl
(primary, secondary, tertiary), vinyl or aryl halides:
i) (CH3)2CHCH(Cl)CH3
ii) CH3CH2CH(CH3)CH(C2H5)Cl
iii) CH3CH2C(CH3)2CH2I
Solution:
i)
ii)
iii)
i) (CH3)3CCH2CH(Br)C6H5
ii) CH3CH(CH3)CH(Br)CH3
iii) CH3C(C2H5)2CH2Br
i)

145
CH3 Br
CH3 CH CH CH3
ii)
4 3 2 1
2-Bromo-3-methylbutane
(2o alkylhalide)
iii)
i) CH3C(Cl)(C2H5)CH2CH3
ii) CH3CH=C(Cl)CH2CH(CH3)2
iii) CH3CH=CHC(Br)(CH3)2
i)
ii)
iii)

146
i) p-ClC6H4CH2CH(CH3)2
ii) m-ClCH2C6H4CH2C(CH3)3
iii) o-Br-C6H4CH(CH3)CH2CH3
i)
ii)
iii)
5. Give the IUPAC names of the following compounds:

i) CH3CH(Cl)CH(Br)CH3
ii) CHF2CBrClF
iii) ClCH2C≡CCH2Br
i)
ii)
iii)

147
6. Give the IUPAC names of the following compounds:
i) (CCl3)3CCl
ii) CH3C(p-ClC6H4)2CH(Br)CH3
iii) (CH3)3CCH=CClC6H4I-p
i)
ii)
iii)

148

i) 2-Chloro-3-methylpentane
ii) p-Bromochlorobenzene
iii) 1-Chloro-4-ethylcyclohexane
Solution :
Structures of the given compounds are:
i)
ii)
iii)

i) 2-(2-Chlorophenyl)-1-iodooctane
ii) 2-Bromobutane
iii) 4-tert-Butyl-3-iodoheptane
Ans: Structures of the given compounds are:
i)
Br
ii) |
CH3 − CH − CH 2 − CH 3
iii)

149
9. Which one of the following has the highest dipole moment?

i) CH2Cl2
ii) CHCl3
iii) CCl4
CH2Cl2 has the highest dipole moment. The reason for it can be understood by looking into the
structure of the given compounds.
i) In CH2Cl2 the resultant of two C – Cl dipole moments is reinforced by resultant of two C – H
diples, therefore, CH2Cl2 (1.62 D) has highest dipole moment.
ii) CCl4 has a perfectly symmetrical structure where the net dipole moment of 4C – Cl is zero.
iii) In CHCl3 the resultant of two C – Cl dipoles is opposed by the resultant of C – H and C – Cl
bonds. Since the latter resultant is expected to be smaller than the former, therefore, CHCl3=
has a dipole moment (1.03D).

150
[PREPARATION OF HALOALKANES AND HALOARENES]

1 MARK QUESTIONS :
1. Write the structure of the major organic product in each of the following reacstions:
i) CH3CH2CH2Cl + NaI 

acetone
heat
→
ii) (CH3)3CBr + KOH 

ethanol
heat
→
Solution :
i) CH3CH2CH2 Cl + Nal 
acetone
∆
→
Propyl chloride
CH 3 -CH 2 -CH 2 -I+NaCl

Iodopropane
ii) ( CH 3 )3 CBr + KOH = 

ethanol
∆
→
tert − Butyl bromide
CH3
|
CH 3 − C = CH 2 + H 2 O + KBr
2 − Methylpropane
2. Write the structure of the major organic product in each of the following reactions:
i) CH3CH(Br)CH2CH3 + NaOH 

Water
→
ii) CH3CH2Br + KCN 
aq.ethanol
→
Solution :
Br
|
i) CH 3CHCH 2 CH 3 + NaOH 
water
→
2-Bromobutane
OH
|
CH 3 − CH − CH 2 CH 3 + NaBr + H 2 O
Butan-2-ol
ii) CH 3CH 2 Br + KCN 

ethanol(aq)
→ CH 3CH 2 CN + KBr
Propanenitrile

151
i) C6H5ONa + C2H5Cl 
→
ii) CH3CH2CH2OH + SOCl2 
→
i) Solution:
ii) CH3CH 2 CH 2 OH + SOCl2 →

Propanol
CH 3CH 2 CH 2 Cl + HCl ↑ + SO 2 ↑
Chloropropane
4. How methyl bromide be preferentially converted to methyl isocyanide?

It can be done by treating the methyl bromide with alcoholic silver cyanide.
2 MARK QUESTIONS :
1. Complete the following reactions by giving the structures:
CH 3 CH3
(i) (ii)
HBr

Peroxide
→  H
Br
→
Solution :
i)
ii)

152
2. Draw the structure of major monohalo product in each of the following reactions:
i) OH 
SOCl2
→
ii) CH2 − CH = CH2 + HBr →

Peroxide
Solution :
i)
ii)
3. Write the mechanism of the following reaction: CH 3CH 2OH 

HBr
→ CH 3CH 2Br + H 2O
Solution :
4. Why is sulphuric acid not used during the reaction of alcohols with KI?
H2SO4 is a strong oxidizing agent. Therefore, when it is used in presence of KI, it tends to
convert KI to HI and finally oxidizes it to I2.
5. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro
compound C5H9Cl in bright sunlight. Identify the hydrocarbon.
Ans: A number of structural isomers are possible for molecular formula C5H10. But, the
given compound gives a single monochloro derivative when reacted with Cl2 in sunlight
suggests that, all the H-atoms in the compound are equivalent. This is possible only if the
compound is a cyclic alkane.
Therefore, the compound is

153
6. How will you bring about the following conversions?

i) Ethanol to but-1-yne
ii) Ethane to bromoethene
(i)
(ii)

i) Propene to nitropropane
ii) Toluene to benzyl alcohol
(i)
(ii)

154
i) CH3CH2CH = CH2 + HBr 
peroxide
→
ii) CH3CH = C(CH3)2 + HBr 
→
i) CH3CH2CH = CH2 + HBr →
peroxide
CH3CH 2CH2 − CH 2 − Br
1-Bromobutane
ii) CH2CH = C ( CH3 ) 2 + HBr 

→
9. How the following conversions can be carried out?

i) tert-Butyl bromide to isobutyl bromide
ii) Aniline to phenylisocyanide
i)
ii)

155
10. 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.
11. Name the alkene which will yield 1-chloro-1-methylcyclohexane by its reaction with HCl.
Write the reactions involved.
1-methylcyclohexene.
12. Give one example of alkene where addition of HBr gives same product in the presence or
absence of peroxide.
Symmetrical alkenes (CH2 = CH2) gives only one addition product,
13. Draw the structures of major monohalo products in each of the following reactions.
Solution :

156
14. In which of the following molecules carbon atom marked with asterisk (*) is asymmetric?
Solution :
and
3 MARK QUESTIONS :
1. Complete the following reaction questions:
i) + HI →
ii) + HBr →
iii) CH3CH2 CH = CH 2 + HBr →
i)
ii)
iii) CH 3CH 2CH = CH 2 + HBr → CH3CH 2 − CH − CH 3

|
Br

157
2. i) Write the structure of major alkene formed by β-elimination of 2, 2, 3-trimethyl-3-

bromopentane with sodium ethoxide in ethanol.
ii) Which one of the compounds in the following pairs is chiral?
``
iii) Identify (A) and (B)in the following:
i)
ii)
Br
Dry ether + 2 NaBr

iii) 2 + 2 Na
Biphenyl
(A)

158
3. a) Identify the chiral molecule in the following pair:
and
(i) (ii)
b) Write the structure of the product when chlorobenzene is treated with methyl chloride in
the presence of sodium metal and dry ether.
c) Write the structure of the alkene formed by dehydrohalogenation of 1-bromo-1-
methylcyclohexane with alcoholic KOH.
a)
b)
c)
4. Among the isomeric alkanes of molecular formula C5H12, identify the one that on
photochemical chlorination yields.
i) A single monochloride
ii) Three isomeric monochlorides.
iii) Four isomeric monochlorides.
Ans: An alkane with molecular formula C5H12 can exist in the following isomeric forms:

159
(I)
(II)
(III)
5. Draw the structures of major monohalo products in each of the following reactions:
i)
ii)
iii)
Ans: The major mono haloderivatives formed in the given reactions are
i)
ii)
iii)

160
6. Draw the structures of major monohalo products in each of the following reactions:
i)
ii) CH3CH2Br + Nal
iii)
Ans: The major mono haloderivatives formed in the given reactions are
i)
ii) H3C – CH2 – I
iii)
7. Write the equations for the preparation of 1-iodobutane from

i) 1-butanol
ii) 1-chlorobutane
iii) but-1-ene.
i) 1-Iodobutane may be prepared from 1-butanol
as: CH3 − ( CH2 )2 − CH2 − OH 
RedP/I2
→ CH3 − ( CH2 ) 2 − CH2 − I
ii) From 1-Chlorobutane
H3C − ( CH2 )2 − CH2 − Cl + HI → CH3 − ( CH2 )2 − CH2 I + NaCl
NaCl formed is precipitated in dry acetone.
iii) From but-1-ene
CH3 − H 2C − CH = CH 2 + HI → CH3 − CH 2 − CH2 − CH2 − I

161
i) Toluene to benzyl alcohol
ii) Benzene to 4-bromonitrobenzene
iii) Benzyl alcohol to 2-phenylethanoic acid
i)
ii)
iii)

162
9. How will you bring the following conversions?

i) Propene to 1 – nitropropane
ii) Toluene to benzyl alcohol
i)
ii)

i) 1 – Chlorobutane to n – octane
ii) Benzene to biphenyl
i)
ii)
11. Why aryl halides cannot be prepared by the reaction of phenol with HCl in the presence of
ZnCl2?
Due to resonance in phenol, C-O bond of phenol has some partial double bond character, which
strengthens the bond. So, it is difficult to break this C–O bond of phenol while the C–O bond of
alcohol is purely single bond and comparatively weaker bond. So, alkyl halides can be prepared
by the reaction of alcohols with HCI in the presence of ZnCl2 while aryl halides cannot be
prepared by the reaction of phenol with HCI in the presence of ZnCl2.

163
[PROPERTIES OF HALOALKANES AND HALOARENES]

2 MARK QUESTIONS :
1. In the following pairs of halogen compounds, which compound undergoes faster SN1
reaction?
C1 C1 C1
i) and ii) and
C1
Solution :
i) SN1- reactivity order is 10 < 20 < 30.
is more reactive than towards SN1 reaction
ii) is more reactive than
2. i) Which is a better nucleophile, a bromide ion or an iodide ion?

ii)Which would undergo SN1 reaction faster in the following pair?
CH3
CH3 CH2 Br and CH3 C CH 3
Br
Solution :
i) Iodide ion is a better nucleophile because of its bigger size and lower electronegativity.
CH3
|
ii) H3C − C − CH3 , as the tertiary carbonium ion formed in the slowest step is more stable than
|
Br
primary carbonium ion.
3. Wurtz reaction fails in case of tertiary alkyl halides. Why?

This is because tert alkyl halides prefer to undergo dehydro halogenation in the presence of
sodium metal instead of undergoing wurtz reaction.
( CH3 )3 C − Br + 2Na 
NaBr
→ ( CH3 )3 C⊙ Na ⊕
ter - butyl bromide ter – butyl sodium

164
4. Write the mechanism of the following SN1
reaction ( CH3 )3 C- Br 

Aq.NaOH
→ ( CH3 ) 3 C- OH + NaBr
5. Give reasons:
i) C – Cl bond length in chlorobenzene is shorter than C – Cl bond length in CH3 – Cl.

ii) SNl reactions are accompanied by racemization in optically active alkyl halides.
i) In halobenzene C – X bond has partial double bond character due to resonance while
CH3 – X bond is single bond.
Thus, bond length of C – X bond in halobenzene is smaller than that in CH3 – X.
ii) In SN1 reaction carbocation intermediate is formed which is a planar molecule, so an

incoming nucleophile can attack from either side and an equimolar mixture of two
components are formed and resulting mixture is optically inactive.

165
6. How do you convert?

i) Chlorobenzene to biphenyl
ii) 2-Bromobutane to but-2-ene.
i)
Br
ii) |
CH 3 − CH − CH 2 − CH 3 
EthanolicKOH
∆
→
2-Bromobutane
CH 3 − CH = CH − CH 3 + HBr
But − 2 − ene
7. Write the major product(s) in the following:

i) 2CH 3 − CH − CH 3 →
Na
Dryether
|
Cl
ii) CH3 − CH 2 − Br 
AgCN
→
i) CH 3 − CH − CH − CH 3
| |
CH3 CH3
ii) CH3CH2NC
8. Give reasons:
i) Racemic mixture is optically inactive.
ii) The presence of nitro group (-NO2) at o/p positions increases the reactivity of haloarenes
towards nucleophilic substitution reactions.
i) Racemic mixture contains equal amount of d-and l-forms, hence rotation due to one
enantiomer is cancelled by another.
ii) The presence of nitro group at o and p-positions withdraws electrons from the benzene ring
and thus, facilitates the attack of the nucleophile on haloarenes. The carbanion thus formed
is further stabilised by resonance.

166
9. Write the structure of the major product in each of the following reactions:
i) CH3 − CH 2 − CH 2 − CH − CH 3 + KOH 
Ethanol
Heat
→
|
Br
ii) +CH3Cl 

anhyd.AlCl3
→
Solution :
i) CH3 – CH2 – CH = CH – CH3
Pent-2-ene (Saytzeff rule)
ii)
10. i) Why is butan-1-ol optically inactive but butan-2-ol is optically active?

ii) Although chlorine is an electron withdrawing group, yet it is ortho-, para-directing in
electrophilic aromatic substitution reactions. Why?
i) Butan-1-o1 is achrial, i.e., does not have chiral ‘C’ atom which is attached to four
different groups, therefore, it is optically inactive.
CH3 – CH2 – CH2 – CH2OH
Butan-1-o1
(Optically inactive)
(No chiral carbon)
Butan-2-o1 is chiral, i.e., has chiral ‘C’ atom, attached to four different groups.
CH3 CH3
H OH HO H
* *
CH2CH3 CH2CH3
d(+) l(-)

167
ii)
Although Cl is electron withdrawing (-1 effect) but still o-and p-directing as due to +R
effect, electron density is maximum at o-and p-positions.
11. i) Which alkyl halide from the following pair is chiral and undergoes faster SN2 reaction?
a) b)
ii) Out of SN1 and SN2, which reaction occurs with
a) inversion of configuration b) racemisation?
i) a) undergoes faster SN2 reaction.
b) is chiral.
ii) a) SN2 reaction occurs with inversion of configuration.
b) SN1 reaction occurs with racemisation.
12. Write chemical equations when

i) ethyl chloride is treated with aqueous KOH.
ii) chlorobenzene is treated with CH3COCl in presence of anhydrous AlCl3.
i) When ethyl chloride is treated with aqueous KOH, ethanol is formed,
CH3CH2Cl + KOH(aq) → CH3CH2OH + KCl
ii)

168
13. i) Which alkyl halide from the following pairs would you expect to react more rapidly by
an SN2 mechanism and why?
CH3 − CH 2 − CH − CH 3
|
Br
CH3 − CH2 − CH 2 − CH2 − Br
ii) Chloroform is stored in closed dark brown bottles.

i) 1-Bromobutane is 1o alkyl halide while 2-bromobutane is 2o alkyl halide. Due to steric
hindrance in 2o alkyl halides, 1o alkyl halide will react faster than 2o alkyl halide in SN2
reaction.
ii) Chloroform when exposed to air and sunlight changes to phosgene which is a poisonous gas.
1
CHCl3 + O 2 → COCl 2 + HCl
2 Phosgene
Thus, it is kept in dark coloured bottles to prevent the oxidation.
14. Write chemical equations when

i) methyl chloride is treated with AgNO2.
ii) bromobenzene is treated with CH3Cl in the presence of anhydrous AlCl3.
i) CH3Cl+AgNO2 → CH3NO2 + AgCl
Br Br Br
CH3
ii) Anhyd. AlCl3

+ CH3Cl +
CH3
15. What are ambident nucleophiles? Explain with an example.

A nucleophile which can attack from more than one centres, is known as ambident nucleophile,
e.g., C ≡ N cyanide ion.
R – X + AgCN→R – NC + AgX
R – X + KCN → R – CN + KX

169
16. Chlorobenzene is extremely less reactive towards a nucleophilic substitution reaction. Give
two reasons for the same.
Haloarenes are much less reactive than haloalkanes towards nucleophilic substitution reactions
due to the following reasons.
i) Resonance effect: In haloarenes the electron pairs on halogen atom are in conjugation with
π-electrons of the ring and the following resonating structures are possible.
C – Cl bond acquires a partial double bond character due to resonance. As a result, the bond
cleavage in haloarene is difficult than haloalkane and therefore, are less reactive towards
nucleophilic substitution reaction.
ii) In halorenes, halogen is attached to sp2-hybridised carbon while in haloalkanes, halogen is
attached to sp3-hybridised carbon.
17. Give reasons for the following:

i) Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
ii) OH + SOCl2 →
i) Since I- is a better leaving group than Br, thus, CH3CH2I undergoes SN2 reaction faster than
CH3CH2Br.
ii)
18. Haloalkanes undergo nucleophilic substitution whereas haloarenes undergo electrophilic

substitution. Explain.
In haloarenes –ve charge gets localised on arenes using resonance, therefore they undergo
electrophilic subsitution.
Haloalkanes have electrophilic carbon centre due to polarity of C – X bond.
170
19. Answer the following:
i) What is known as a racemic mixture? Give an example.
ii) Of the two bromo derivatives, C6H5CH(CH3)Br and C6H5CH(C6H5)Br, which one is more
reactive in SN1substitution reaction and why?
i) An equimolar mixture of a pair of enantiomers is called racemic mixture. A racemic mixture
is optically inactive due to external compensation.
CH 3 − CH − CH 2 − CH 3
Example: |
OH
Butan-2-o1(50% mixture of d-and-1-form)
ii) Of the two bromo derivatives, C6H5CH(C6H5) Br is more reactive than C6H5CH(CH3)Br for
SN1 reaction because its carbocation is resonance stabilised by two phenyl groups.
20. Write the mechanism of the following reaction:
n − BuBr + KCN 

EtOH,H 2O
→ n − BuCN
Ans: Normal butyl bromide will give SN2 reaction:

171
21. In the following pairs of halogen compounds, which compound undergoes faster SN1
reaction?
i) and
ii) and
SN1 reaction proceeds via the formation of a carbocation intermediate. This intermediate is
formed by the cleavage of the C – X bond. More stable is the resultant carbocation faster is the
SN1 reaction.
3o carbocation > 2o carbocation > 1o carbocation
i) will react faster. The carbocation will be more stable and hence
reaction will be faster.
ii) reacts faster due to the greater stability of 2o carbocation as
compared to 1o carbocation.
22. Which compound in each of the following pairs will react faster in SN2 reaction with OH-?
i) CH3Br or CH3I
ii) (CH3)3CCl or CH3Cl
i) Between CH2Br and CH2I, CH3I will react faster via the SN2 mechanism. In SN2 mechanism,
C – X bond breaks and the faster it breaks faster is the reaction.
I- is a better leaving group. Owing to its large size, the C – 1 bond breaks faster than the C –
Br bond and reaction proceeds further at a greater rate.
ii) The order of reactivity in an SN2 reaction depends on minimal steric hindrance around the
carbon involved in the C – X bond. Lesser the steric hindrance faced by the incoming
nucleophile, more reactive will be the alkyl halide towards SN2 reaction.
Based on this, CH3Cl will react faster than (CH3)3CCl.
172
23. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH.
C6H5CHClC6H5 is hydrolysed faster.
i) Hydrolysis of an alkyl halide is an example of nucleophilic substitution reaction. In case of
aryl halides this follows the SN1 pathway i.e., via the formation of carbocation.
ii) C6H5CH2Cl or benzyl chloride gives
CH2 (I) carbocation while
iii) Out of I & II, carbocation II is more stable. The reason is the presence of two phenyl rings
attached to the carbon carrying the positive charge.
iv) As a result, the delocalization of the +ve charge is greater and the carbocation is more stable.
Due to this, (II) is formed faster and the corresponding halide is hydrolysed with greater ease
as compared to benzyl chloride.
24. Write the structure of an isomer of compound C4H9Br, which is most reactive towards SN!
reaction?
Tertiary (3o) alkyl halides are most reactive towards SN1 reactions followed by secondary (2o)
and primary (1o) alkyl halides. C4H9 Br has four isomers:
As 3o alkyl halides form a more stable 3o carbocation intermediate than secondary and primary
alkyl halides which form 2o and 1o carbocation, respectively.
CH 3
|
Hence, the isomer, CH 3 − C − Br (2-bromo-2-methyl propane) of compound C4H9 Br is most
|
CH 3
reactive towards SN1 reactions.

173
25. Out of chlorobenzene and benzyl chloride, which one gets easily hydrolysed by aqueous
NaOH and why?
C–Cl bond in chlorobenzene is stronger than C–Cl bond in benzyl chloride. Therefore hydrolys
is of benzyl chloride is easy. It is due to the fact that in chlorobenzene the lone pairs of
electrons on halogen atom are delocalized as shown below
Due to this C– Cl bond have some double bond character. Whereas in benzyl chloride C– Cl
bond is weak. Cleavage of C– Cl bond in benzyl chloride forms benzyl cation which is stable
due to resonance as shown below:
26. Elimination reactions (especially β-elimination) are as common as the nucleophilic

substitution reaction in case of alkyl halides. Specify the reagents used in both cases.
Elimination reactions are as common as the nucleophilic substitution reaction in case of alkyl
halides as two reactions occur simultaneously. Generally, at lower temperature and by using
weaker base, nucleophilic substitution reactions occur while at higher temperature and by using
a stronger base, elimination reactions (especially β-elimination) take place.
e.g. If ethyl bromide is treated with aq. KOH at low temperature, it gives ethanol while if it is
treated with alcoholic KOH at high temperature then it gives ethene.

174
27. Bring out the following conversions.

i) Chlorobenzene to 2-chloroacetophenone
ii) Chloroethane to butane
Solution :
3 MARK QUESTIONS :
1. i) Out of (CH3)3C – Br and (CH3)3C – I, which one is more reactive towards SN1 and why?
ii) Write the product formed when p-nitrochlorobenzene is heated with aqueous NaOH at 443
K followed by acidification.
iii) Why dextro and laevo-rotatory isomers of Butan-2-ol are difficult to separate by fractional
distillation?
i) (CH3)3 C – I is more reactive because C – I bond has the minimum bond dissociation
enthalpy.
ii)
iii) Dextro and lawvo-rotatory isomers of butan-2-ol are difficult to separate by fractional
distillation because they have almost same boiling point.

175
2. Following compounds are given to you:

2-Bromopentane, 2-Bromo-2-methylbutane, 1-Bromopentane
i) Write the compound which is most reactive towards SN2 reaction.
ii) Write the compound which is optically active.
iii) Write the compound which is most reactive towards β-elimination reaction.
i) 1-Bromopentane
ii) 2-Bromopentane
iii) 2-Bromo-2-methylbutane
3. Answer the following questions:

i) What is meant by chirality of a compound? Give an example.
ii) Which one of the following compounds is more easily hydrolysed by KOH and why?
CH3CHClCH2CH3 or CH3CH2CH2Cl
iii) Which one undergoes SN2 substitution reaction faster and why?
(or)
i) The molecules which are not superimposable on their mirror images are called chiral
molecules. The property of non-superimposability of a structure on its mirror image is
called chirality.
ii) CH 3CH 2 CHCH3 hydrolyses easily with KOH because it is secondary halide.
|
Cl
iii) As iodide is a better leaving group because of its large size, therefore,
undergoes SN2 reaction faster than

176
4. Rearrange the compounds of each of the following sets in order or reactivity towards SN2
displacement:
i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-bromo-2-methylbutane
iii) 1-Bromobutane, 1-Bromo-2, 2-dimethyl propane, 1-Bromo-2-methylbutane
i) 1-Bromopentane > 2-Bromopentane < 2-Bromo-2-methylbutane.
ii) 1-Bromo-3-methylbutane > 3-Bromo-2-methylbutane>2-Bromo-2-methylbutane.
iii) 1-Bromobutane > 1-Bromo-2-methylbutane > 1-Bromo-2,2-dimethylpropane.
5. a) Write a chemical test to distinguish between:

i) Chlorobenzene and benzyl chloride
ii) Chloroform and carbon tetrachloride
b) Why is methyl chloride hydrolysed more easily than chlorobenzene?
a) i) Benzyl chloride gives white precipiate with AgNO3 solution while chlorobenzene does
not.
ii) CHCl3 with aniline in presence of alc. KOH gives foul smelling isocyanides whereas
CCl4 does not.
b) CH3Cl is hydrolysed easily than C6H5Cl as chlorobenzene has partial double bond
character between C – Cl bond which is difficult to break.
6. Write the structures of the following compounds:

i) 2-Chloro-3-methylpentane
ii) 1-Chloro-4-ethylcyclohexane
iii) 4-tert-Butyl-3-iodoheptane
i)
ii)
iii)

177
7. Which alkyl halide from the following pairs would you expect to react more rapidly by an SN2
mechanism? Explain your answer.
i)
ii)
iii)
We know that SN2 mechanism involves a transition state wherein both, the incoming
nucleophile as well as the leaving group are present around the carbon atom. There are 5
atoms simultaneously bonded to it.
Thus, for such a transition state to be possible, there should be minimum steric hindrance.
Hence, 1o alkyl halides are most reactive towards SN2 followed by 2o and finally 3o.
1o RX > 2o RX > 3o RX
Based on the above order,
i) CH3CH2CH2CH2Br is more reactive.
ii) is more reactive.
iii) is more reactive.
In (iii), it is the proximity of the branched chain – CH3 that determines the reactivity.
In the methyl group is closer to the leaving group thereby
hindering the transition state.
8. Identify A, B, C, D, E, R and R′ in the following.
i)
R Br + Mg dry ether D2O

ii) C CH3CHCH3
D
178
iii)
i)
ii) R is
iii) R′ is

179
9. Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with
sodium ethoxide in ethanol and identify the major alkene:
i) 1-Bromo-1-methylcyclohexane
ii) 2-Chloro-2-methylbutane
iii) 2,2,3-Trimethyl-3-bromopentane.
i)
ii) +
iii)

i) Propene to propyne
ii) Ethanol to ethyl fluoride
iii) Bromomethane to propanone
i)

180
ii)
iii)

i) But-1-ene to but-2-ene
ii) 1-Chlorobutane to n-octane
iii) Benzene to biphenyl.
i)
ii)
iii)

181
12. Explain why

i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
ii) alkyl halides, though polar, are immiscible with water?
iii) Grignard reagents should be prepared under anhydrous conditions?
i) a) In order to understand the lower dipole moment of chlorobenzzene we need to look
into the contributing structures of the molecules.
b) From the above structures we find that the C – Cl bond in chlorobenzene has a
partial double bond character (structure II, III and IV). As a result, the C – Cl bond
length here is shorter than the C – Cl single bond but longer than the C – Cl double
bond.
c) Also evident is the positive charge on Clatom which reduces the partial negative
(δ-) charge which it is expected to carry by the virtue of its electronegativity.
d) Consequently, the dipole moment, which is a product of bond length and partial
negative charge on Cl atom, reduces.
However, in cyclohexyl chloride this does not happen. It is an alkyl halide and
carbon is purely sp3 hybridized and C – Cl bond has the bond length of a single
bond and δ- appearing on Cl is also higher, thus, the greater dipole moment.
ii) Only those compounds which can form hydrogen bonds with water are miscible with
it. Alkyl halides, though polar due to the presence of electronegative halogen atom,
are immiscible since they cannot form hydrogen bonds.
182
iii) Grignard reagents R – Mg – X is a class of highly reactive compounds which can

extract a proton even from water molecule. They thus, turn into the corresponding
alkanes and render any other desired reaction ineffective.
This is why Grignard reagents are prepared in the absolute absence of water
(anhydrous conditions). (e.g.,)

i) Propene to propan-1-ol
ii) Ethanol to but-1-yne
iii) 1-Bromopropane to 2-bromopropane
i) CH 3 − HC = CH 2 →
HBr /
Peroxide
Propene
aq.KOH/ ∆
CH3 − CH2 − CH2 Br  →
CH3 − CH 2 − CH 2 − OH
Propanol
ii) 2CH3CH 2OH + SOCl2 →

2CH3CH2Cl + SO2 ↑ +HCl ↑
alc.KOH/ ∆
CH3CH2Cl  → CH2 = CH2
alc.KOH/ ∆
→
Br2 CCI4
CH 2 − CH 2  →
| |
Br Br
HC ≡ CH NaNH 2
liq.NH 3. 196K
→ HC ≡ CNa
CH3 − CH2 − Cl + NaC ≡ CH 

→
CH3 − CH 2 − C ≡ CH
But − 1 − yne
iii) CH 3CH 2 CH 2 Br 

C 2 H5 O/ KOH
∆
→
1-Bromopropane
CH3CH = CH2  
HBr
→
CH 3 − CH − CH3
|
Br
2-Bromopropane
183

i) Ethanol to propanenitrile
ii) Aniline to chlorobenzene
iii) 2-Chlorobutane to 3, 4-dimethylhexane
i) H 3C − CH 2OH SOCl 2
→ H 3C − CH 2Cl
Ethanol
KCN/EtOH − H2 O
 → CH 3 − CH 2 CN
Propanenitrile
ii)
iii) 2CH3 − CH 2 − CH − Cl + 2Na →

dry ether
|
CH3
2-Chlorobutane
CH 3 − CH 2 − CH − CH − CH 2 − CH 3 + 2NaCl
| |
CH 3 CH 3
3,4-Dimethylhexane

i) 2-Methyl-1-propene to 2-chloro-2-methylpropane
ii) Ethyl chloride to propanoic acid
iii) But-1-ene to n-butyliodide
i)
ii) CH3 − CH 2Cl KCN

EtOH − H 2 O
→ CH3 − CH 2 CN 
H2O
→ CH3CH 2COOH
iii) CH 3 − H 2 C − HC = CH 2 
HBr
peroide
→ CH3 − CH 2 − CH 2 − CH 2 − Br
→
Nal
CH 3CH 2 CH 2 CH 2 + NaCl
n-Butyliodide

184

i) 2-Chloropropane to 1-propanol
ii) Isopropyl alcohol to iodoform
iii) Chlorobenzene to p-nitrophenol
Cl
i) |
CH3 − CH − CH3 
KOH/C2 H5 OH
∆
→
CH3 − CH = CH2 
HBr,peroxide
→
CH3 − CH 2 − CH 2 = Br

KOH /H 2 O
∆
→ CH 3 − CH 2 − CH 2 − OH
Propanol
ii)
iii)

i) 2-Bromopropane to 1-bromopropane
ii) Chloroethane to butane
iii) Benzene to diphenyl
i) H3C − CH = CH2 
HBr/peroxide
→
H 3C − CH 2 − CH 2 − Br
1-Bromopropane

185
ii) 2H 3C − CH 2 − Cl + 2Na →

dry ether
Chloroethane
H3C − CH2 − CH 2 − CH3 + 2NaCl

Butane
iii)
18. Primary alkyl halide C4H9Br (A) reacted with alcoholic KOH to give compound (B). Compound
(B) is reacted with HBr to give (C) which is an isomer of (A). When (A) is reacted with sodium
metal it gives compound (D), C8H18 which is different from the compound formed when n-butyl
bromide is reacted with sodium. Give the structural formula of (A) and write the equations for all
the reactions.
The given reaction sequence is:
When (A) is treated with Na metal, Wurtz reaction takes place.

It is given that (A) is a primary alkyl halide.
∴The possible structures of C4H9Br(A) are
H 3C − CH − CH 2 Br
I. |
CH 3
II. CH 3 − CH 2 − CH 2 − CH 2 − Br
However, it is given that (A) on reaction with Na metal gives alkane C8H18which is not same
as the one obtained from the Wurtz reaction of n-butylbromide. Therefore (A) ≠ I.
Thus,

186
19. i) Why are alkyl halides insoluble in water?

ii) Why is butan – 1 – ol optically inactive but butan – 2- ol is optically active ?
iii) Although chlorine is an electron withdrawing group, yet it is ortho, para directing in
electrophilic aromatic substitution reactions. Why?
i) Due to the inability of alkyl halide molecule to form intermolecular hydrogen bonds with
water molecules
OH
|
ii) CH 3 − CH 2 − C − CH 3 Due to the presence of a chiral carbon butan – 2 – ol is an optically
|
H
active compound.
But butan -1- ol has no chiral carbon & hence it is optically inactive.
CH3 − CH2 − CH2 − CH2 − OH
iii) As the weaker resonance (+R) effect of ‘Cl’ which stabilises the carbocation formed tends
to oppose the stronger inductive (-I) effect of ‘Cl’ which destabilize the carbocation at ortho
and para positions and makes deactivation less for ortho and para position .

187
20. How do you convert
i) Chlorobenzene to toluene? ii) but -1- ene to but -2-ene?
iii) ethanol to ethyl iodide?
i)
Wurtz - fitting reaction
ii)
Re d − p + I
iii) 3 CH 3 − CH 2 − OH ( PI ) 
3
→ 3 CH 3 − CH 2 − I + H 3 PO 3
2
Ethanol

Water
→
i) CH3 CH(Br)CH2CH3+ KOH
ii) CH3CH2 Br +KCN  →

Aq.ethanol
iii) C6H5ONa+C2H5Cl →
i)
ii)
⊕
iii) C6 H 5O Na + C 2 H 5 − Cl → C6 H 5 − O − C 2 H 5 + NaCl
⊙ williamson 's
synthesis
phenetole

188

i) Propene to propyne
ii) Ethanol to ethyl fluoride
iii) Bromomethane to propanone
i)
ii)
iii) CH 3 − Br + alc KCN → CH 3 − CN  →→

CH MgBr 3
ether
↓
Bromomethane
+
CH 3 − C = O ←
H3O
− NH3
 CH 3 − C = NMgBr
− MgBr(OH)
| |
CH 3 CH 3
Pr opanone
23. Which alkyl halide from the following pairs would you expect to react more rapidly by an SN1
mechanism? Explain your answer.
CH3
CH 3 CH 2 CH 2 Br or CH 3 CH 2 CHCH 3 CH 3CH 2 CHCH 3 H3C C

| ii) | (or) Br
Br
i) Br CH 3
CH 3CHCH 2 CH 2 Br or CH 3CH 2 CHCH 2 Br

iii) | |
CH 3 CH 3
SN1 reactivity order of alkyl halides is 1° < 2° < 3°

i) CH3 − CH 2 − CH − CH3 , being secondary halide, can give more stable carbocation.
|
Br
189
CH 3
|
ii) CH 3 − C − Br is more reactive due to tert.carbocation stability
|
CH 3
CH 3
|
CH 3 − C − ⊕ CH 3 − CH 2 − CH − CH 3
| > ⊕
CH 3 2°
3°
iii) CH3 − CH 2 − CH − CH 2 − Br is more reactive towards SN1 .

|
CH3
CH3 − CH − CH 2 − CH 2 − Br
but | is less reactive towards SN1 due to β - branching.
CH3
24. Give reasons for the following

i) tert –Butyl chloride reacts with aqueous sodium hydroxide by SN1 mechanism while n–
butyl chloride reacts by SN2 machanism.
ii) Vinyl chloride is unreactive in nucleophilic substitution reactions.
iii) 3 – Bromocyclohexene is more reactive than 4 – bromocyclohexene in hydrolysis with
aqueous NaOH.
i) Since tert - butyl Chloride can give stable 3° - butyl cabocation n - butyl chloride reacts by
SN2 - mechanism because ‘C’ of C - Cl bond is less crowded and favourable for nuclephile
to attack from back side resulting in the formation of transition state
ii)
due to resonance C - Cl bond is getting partial double bond character, which makes C - Cl
bond stronger & hence it is difficult cleave it than the C - Cl single bond
iii) 3 - bromocyclohexene is an allylic halide and high reactivity of this is due to
resonance stabilization of carbocation

190
25. Give reasons for the following :

i) p-Dichlorobenzene has higher melting point and lower solubility than o – and m – isomers
ii) Benzyl chloride undergoes SN1 reaction faster than cyclohexyl methylchloride.
i) The P - isomer being more symmetrical fits closely in the crystal lattice and thus has stronger
intermolecular forces of attraction than o - and m -isomers. As during melting or dissolution,
the crystal lattice breaks, therefore, a larger amount of energy is needed to melt or dissolve
the P - isomer than the corresponding o - and m - isomers.
ii) Because in case of benzylchloride, the carbocation formed after the loss of Cl- is stabilized by
resonances where as, no such stabilization is possible in the carbocation obtained
from cyclohexyl methylchloride
26. Explain why

i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
ii) alkyl halides, though polar, are immiscible with water?
iii) Grignard reagents should be prepared under anhydrous conditions?
less - ve charge more - ve charge
+ -
-
i) Cl
+
Cl
SP2 - hybrid carbon

SP3- hybrid carbon
Chlorobenzene
sp 2 − C sp 3 − C
%S-
33.3% 25%
EN sp2 - C > sp3 - C
-ve charge on chlorine atom
C - Cl bond has partial double bond Character.

191
∴ Bond length of C - Cl bond decreases
Cl < Cl
As dipolemoment is a product of charge and distance therefore, dipolemoment of

chlorobenzene is less than that of cyclohexyl chloride.
ii) Alkylhalides, though polar, are immiscible in water because they are unable to form hydrogen
bonds with water molecules
iii) Grignard reagents are very reactive. They react with moisture present in the apparatus or the
starting materials to give hydrocarbons
δ− δ⊕
→ R − H + MgX ( OH )
R − Mg X + H 2O 
Hence Grignard reagent must be prepared under anhydrous conditions
27. Write the major products (s) in the following reactions:

i) 
PCl5
→ ii) H −Br
CH2 OH
 →
CH3
OH
iii) CH3CH2Cl 

KNO2
→?
i)
ii)
iii) CH 3 − CH 2 − Cl 
KNO2
→ CH 3 − CH 2 − ONO

192

i) Benzene to 4 – bromonitrobenzene
ii) Benzene to biphenyl
iii) tert. Butyl bromide to isobutyl bromide
i)
ii)
iii)
29. i) Which compound in each of the following pairs will react faster in SN2 reaction with OH–
a) CH3Br or CH3I b) ( CH3)3 CCl or CH3Cl
ii) Out of C6H5CH2Cl and C6H5CHClC6H5 which is more easily hydrolysed by aqueous KOH?
i) a) CH3 I reacts faster than CH3Br in SN2 reaction with OH- ion, since I- ion is a better leaving
group than Br- ion.
b) On steric grounds, 1o - alkyl halides are more reactive than ter - alkyhalides in SN2
reactions. Hence CH3 - Cl will react at a faster rate than (CH3)3CCl in a SN2 reaction with
OH- ion.
ii) C6H5 - CH2Cl is a 1o - aralkylhalide while C6 H5 − CH − C6 H5 is a 2° aralkylhalide.
|
Cl
⊕
→ C6 H 5 − CH − C6 H 5 + Cl −
C6 H 5 − CH − C6 H 5 
|
Cl
Stabilised by delocalization over two phenyl ring
⊕
→ C 6 H 5 − CH 2 + Cl −
C 6 H 5 − CH 2 − Cl 
Stabilised by delocalization over one phenyl ring
193
30. Predict the alkenes that would be formed by dehydrohalogenation of the following halides
with sodium ethoxide in ethanol and identify the major alkene.
i) 1 - Bromo - 1- methylcyclohexane
ii) 2- Chloro - 2 - methylbutane
iii) 3 - Bromo – 2, 2, 3 – trimethylpentane.
i)
ii)
iii)
31. Complete the following reactions by giving the structures of major organic products.
i) (CH3 )3 C − Br 
Mg
→....... 
H 2O
→......
ii) (CH3 )3 C − CH2 − Br 
C H ONa /C H OH
2 5 2
→............
5
iii) + ( C H 3 ) 3 C − C H 2 − B r  a   → ............
n h y d . A IC I 3
Solution :
CH 3 CH 3 CH 3
| | |
i) CH 3 − C − Br →
Mg
CH 3 − C − MgBr 
H2O
→ H 3C − C − H
| | |
CH 3 CH 3 CH 3
2 − methyl propane
CH 3 CH 3
| |
ii) H 3C − C − CH 2 − Br 
C 2 H 5 ONa / C2 H 5 OH
∆
→ H 3C − C − CH 2 − O − CH 2 − CH 3
| |
CH 3 CH 3
Ethylneopentyl ether

194
CH3 CH3
| |
iii) CH3 − C − CH 2 − Br anhy AlCl3
1, 2 − methyl shift
→ H 3 C − C − CH 2 − CH 3
|
CH 3
1, 1-Dimethyl
propyl benzene
4 MARK QUESTIONS :
1. The polarity of C – X bond is responsible for the nucleophilic substitution reactions of alkyl
halides which mostly occur by SN1 & SN2 mechanisms. The rates of SN1 reaction are
governed by the stability of intermediate carbocations while that of SN2 reactions are
governed by steric factors. Chirality has a great role in understanding, the mechanism of SN1
& SN2 reactions. SN1 reactions of chiral alkyl halides are accompanied by racemisation.
Whereas SN2 reactions are characterized by inversion of configuration.
i) What do you mean by chirality?
ii) Which of the following compounds undergo SN1 reaction faster and why?
iii) In the pair, (CH3)3 C – Br & CH3 – CH2 – Br which will react faster in SN2 reaction and
why?
iv) What is meant by the term racemic mixture?
v) Predict the order of reactivity of the four isomeric bromobutanes in SN1 and SN2
reactions.
Solution :
i) The objects which are non-super imposable on their mirror images are called chiral and the
property is known as chirality.
ii) Benzyl chloride undergoes SN1 reaction faster than cyclohexyl methyl chloride because in
case of benzyl chloride, the carbocation formed after the loss of Cl- is stabilized by resonance.
iii) CH3 – CH2 – Br is more reactive towards SN2 reaction than (CH3)3 C – Br
∵ SN2 reactivity order 1o > 2o > 3o (due to stearic crowd)
iv) An equimolar mixture of a pair of enantiomers is known as racemic mixture.

195
v) SN1 reactivity order
SN2 reactivity order
2. Grignard reagents are alkyl magnesium halides. Due to large electro negativity difference
between carbon & magnesium, the carbon-magnesium bond has significant ionic character.
The hydrocarbon part of the Grignard reagents act as a source of carbanion. Therefore,
Grignard reagents readily, undergo nucleophilic addition reactions to aldehydes & ketones
forming, the addition products which upon hydrolysis yield alcohols.
i) Give the mechanism of addition of Grignard reagent to carbonyl compound forming
an alcohol.
ii) How will you convert propanone to 2-methylpropan-2-ol.
iii) Write the structures of A & B in the following reactions.
CH 3 − CH 2 − OH 
Cu
573K
→ A →
1) CH3 MgBr
2) H 2 O
B
iv) Write the structures of A & B in the following reactions.
Mg
dry ether
→ A 
1) CO 2
2) H O +
→B
3
v) What will be the product formed when chlorobenzene reacts with magnesium in
presence of dry ether.
Solution :
i)

196
ii)
O OH
|| |
CH 3 − CH 2 − OH 
Cu
573k
→ CH 3 − C − H 
(p) CH 3 MgBr
(q) H 2 O
→ CH 3 − CH
iii) (A) (B) |
CH 3
Ethanal 2 − propanol
iv)
v)
[POLYHALOGEN COMPOUNDS]
2 MARK QUESTIONS :
1. Give the uses of freon 12, DDT.
i) Freon 12 (CCl2F2) is
• used in aerosol propellants
• refrigeration
• air conditioning
ii) DDT (dichlorodiphyenyltrichloroethane) is
• used as an insecticide,
• mainly used against mosquitos
197
2. Carbon tetrachloride and iodoform.

i) Carbontetrachloride (CCl4) is used
• in manufacture of refrigerants and propellants for aerosol cans
• in synthesis of chlorofluorocarbons
• as cleansing agent
• as a solvent in laboratories
ii) Iodoform (CHI3) is
• used as an antiseptic.
• used for sterilizing instruments used for surgery
3. Write one use for each of the following

i) DDT ii) Iodoform
i) As an antiseptic
ii) Powerful insecticide
4. Which polyhalogen compound is used in the production of freon refrigerant R-22?

Chloroform (CHCl3)
5. Name the non-volatile, non-toxic compound, which is formed when 1% ethanol is added to
the bottles of chloroform to convert phosgene gas to that compound.
Diethyl carbonate
6. Chloroform is stored in closed dark coloured bottles completely filled, so that air is kept out.
Explain.
In the presence of light, chloroform is oxidised by air to form an extremely poisonous gas,
phosgene (carbonyl chloride). It is therefore, stored in dark coloured completely filled bottles,
so that air is kept out.
7. Iodoform has antiseptic properties. Give one reason to support it.

The antiseptic properties of iodoform is due to free I2, which is liberated when iodoform comes
in contact with skin.

198
8. i) Give the reaction for the formation of phosgene gas.

ii) What happens when phosgene gas reacts with ethanol? (Give chemical reaction only)
3 MARK QUESTIONS :
1. Give reasons for the following :
i) Chloroform is stored in closed dark coloured bottles.
ii) Chloroethane is insoluble in water.
iii) Thionyl chloride method is preferred for preparing alkyl chlorides from alcohols.
Solution :
i) Because chloroform is oxidized by air in the presence of light to an extremely poisonous gas
phosgene
ii) Chloroethane is unable to form hydrogen bonds with water. Hence it is insoluble in water.
iii) The by products of the reaction i.e SO2 and HCl being gases escape into the atmosphere
leaving behind alkyl chlorides in almost pure state
4 MARK QUESTIONS :
1. Name the following polyhalogen compounds.
i) Compound that act as a propellant in aerosols.
ii) Compound that is used in the preparation of chloropicrin.
iii) Compound that act as fire extinguisher.
iv) Compound that is a cheap insecticide.
v) Compound that is used in hair sprays.
Solution :
i) Carbon tetrachloride (CCl4)
ii) Chloroform (CHCl3)
iii) Carbon tetrachloride (CCl4)
iv) DDT
v) Freons
199
ALCOHOLS, PHENOLS AND ETHERS

[ALCOHOLS]
1 MARK QUESTIONS :
1. Name the primary alcohol which gives iodoform test.
CH 3 − CH 2 − OH can give iodoform test
(ethanol)
2. Name the reagent used in the following reaction

CH3 − CH = CH − CHO 
?
→ CH3 − CH = CH − CH2 − OH
Solution :
LiAlH4 - Lithium aluminium hydride
NaBH4 - Sodium borohydride
CH 3 − CH = CH − CHO 
LiAlH 4 (or) NaBH 4
→ CH 3 − CH = CH − CH 2 − OH
3. Write the IUPAC name of neo-pentyl alcohol.

CH 3
|
H 3C − C − CH 2 − OH
|
CH 3
Solution :
2, 2-Dimethylpropan-1-ol
4. Write the IUPAC name of the following compound:
Solution :
3-phenylprop-2-en-1-ol
5. How will you distinguish between methyl alcohol and ethyl alcohol?
By iodoform test on heating with I2 and NaOH
Methyl alcohol – No yellow compound is formed
Ethyl alcohol – Yellow compound (CHI3) with characteristic odour is formed
6. How would you convert ethanol to ethene?

200
7. How will you synthesise the following alcohol from appropriate alkene:
Solution :
8. Why Cl – CH2 – CH2 – OH is a stronger acid than CH3 – CH2 OH?

Due to – I effect of chlorine, it stabilizes the alkoxide ion
stability
CH 3 − CH 2 − O − < CH 2 − CH 2 − O −
|
Cl
9. Explain why propanal boils at a higher temperature than butane?

In propanol there is intermolecular H- bonding but in propane, there is no H- bonding
O − H − − − − −O−H − − − − O − H
| | |
C3 H 7 C3 H 7 C3H 7
10. How is that alcohol and water are miscible in all proportions?
Due to intermolecular H- bonding alcohol and water are miscible in all proportions
11. What is the IUPAC name of glycerol?

CH 2 − CH − CH 2
| | | Propane – 1, 2, 3, - triol
OH OH OH
12. Why can’t rectified spirit be converted into absolute alcohol by simple distillation?
Rectified spirit forms an azeotropic mixture which distills at 351.3K.
13. Suggest a reagent for the following conversion.
⊕
−
PCC = Pyridinium chlorochromate C6 H5 N H CrO3Cl (or) CrO3 = Chromium trioxide.
201
14. Predict the major product of acid catalysed dehydration of

i) 1-Methylcyclohexanol and
ii) Butan-1-ol
Solution :
i)
CH 3CH 2 CH 2 CH 2 OH 
Dehydration
H+
→ CH 3CH = CHCH 3 + H 2 O
ii) Butan - l - ol But - 2 - ene
(Major product)
15. Write the IUPAC name of the following compounds.
A) B)
Solution :
A) 3-Ethyl-5-methylhexane-2, 4-diol.
B) 1-Methoxy-3-nitrocyclohexane.
16. Suggest a reagent for conversion of ethanol to ethanoic acid.

i) CrO3 – H2SO4 ii) KMnO4/OH– iii)Acidified KMnO4 or K2Cr2O7
17. Suggest a reagent for the following conversion:
Solution :
CrO3, Pyridine and HCl (Pyridinium chlorochromate-PCC)
18. What is the order of dehydration of primary, secondary and tertiary alcohols?
Tertiary alcohols > Secondary alcohols > Primary alcohols

202
2 MARK QUESTIONS :
1. How will you convert:
i) Propene to Propan-1-ol?
ii) Ethanal to Propan-2-o1?
2. Answer the following questions.

i) Among HI, HBr, HCl; HI is most reactive towards alcohols. Why?
ii) Of the two alcohols; (a) CH2=CH–CH2OH and (b) CH2=CH–CH2–CH2OH, which one will
react more easily with conc. HCl in the presence of ZnCl2?
Solution :
i) HI has the lowest bond dissociation energy due to longer bond length that is why it is most
reactive.
ii) CH2=CH–CH2OH
3. How can you convert Propan-1-ol into Propan - 2- ol
4. How will you convert ethylalcohol into isopropyl alcohol?
5. How can you convert ethanol into ethylene glycol? (in two steps)

203
6. Arrange the four isomeric butyl alcohols in order of increasing solubility in H2O.
As branching increases, the surface area of the non-polar hydrocarbon part decreases and hence,
the solubility increases with branching.
Thus,
Butan -1-ol < 2-Methylpropan-1-ol < Butan-2-ol < 2-Methylpropan-2-ol.
7. Name the reagent required for converting methyl magnesium iodide to n-propyl alcohol.
Ethylene oxide is used to convert CH3MgI to CH 3 − CH 2 − CH 2
|
OH
8. What is denatured alcohol?

Alcohol is made unfit for drinking purpose by mixing some poisonous compounds like
methanol (or) copper sulphate and pyridine in it. This is called denatured alcohol.
9. What happens when (CH3)3C–OH is treated with Cu at 573 K,
10. Give reasons for the following:

The C—O—H bond angle in alcohols is slightly less than the tetrahedral angle (109o28′).
Solution :
It is due to the repulsion between the lone pair of electrons on oxygen atoms,

204
11. Write the reactions involved in the preparation of ethylalcohol from sucrose by fermentation.
C12 H 22 O11 + H 2 O 
Invertase
→ C6 H12 O 6 + C6 H12 O 6
Sucrose Glucose Fructose
C6 H12 O6 
Zymase
→ 2C2 H5OH + 2CO2
Glucose (or)
Fructose
12. How can propan - 2 - one be converted into tert - butylalcohol?
13. Why is the reactivity of all the three classes of alcohols with con HCl and ZnCl2 (Lucas
reagent) different?
An alcohol reacts with conc HCl and ZnCl2 (Lucas reagent) to give an intermediate carbocation.
More stable is the carbocation, faster is the reaction.
Stability order of carbocations 3o > 2o > 1o.
So the reactivity of alcohols towards Lucas reagent is
Tertiary alcohol > Secondary alcohol > Primary alcohol.
14. Explain why low molecular mass alcohols are soluble in water.
Alcohols are soluble in water due to H - bonding. Low molecular mass alcohols are more
soluble in water than higher alcohols. This is, due to increase in molecular mass, the
hydrophobic part (H2O hating) of the alcohols increases. This reduces their water solubility.
15. Give reason for the higher boiling point of ethanol in comparison to methoxy methane.
Ethanol undergoes intermolecular H-bonding due to the presence of -OH group, resulting in the
association of molecules. Extra energy is required to break these hydrogen bonds. On the other
hand, methoxymethane does not undergo H-bonding.
Hence, the boiling point of ethanol is higher than that of methoxymethane

205
16. Show how are the following alcohols-prepared by the reaction of a suitable Grignard reagent
on methanal?
i) ii)
i)
ii)
17. Write the structures of the isomers of alcohols with molecular formula C4H10O. Which of
these exhibits optical activity?
The structures of the isomers of alcohols C4H10 are :
i) CH3CH2CH2CH2OH ii) CH3 - CH - CH 2OH
|
CH 3
Butan-1-ol(1o) 2-Methylpropan-1-ol(1o)
CH 3 - CH - CH 2 CH 3 CH 3 - C - CH 3
iii) | iv) |
OH OH
Butan-2-ol(2o) 2-Methylpropan-2-ol(3o)
Butan-2-ol is optically active
18. How would you obtain 2-Methylpropene from 2-Methylpropanol?

206
3 MARK QUESTIONS
1. A compound ‘A’ is optically active. On mild oxidation, it gives a compound ‘B’ but on
vigorous oxidation gives another compound ‘C’. C along with D is also formed from B by
reaction with iodine and alkali. Deduce the structures of A, B, C, D.
2. How would you obtain the following?

i) 2-Methylpropan-2-ol from methylmagnesium bromide
ii) Propan-2-ol from propene
Solution :
i)
ii)
3. i) Write the formula of reagent used in the following reaction:

Hydroboration of propene and then oxidation to propanol.
ii) Arrange the following compound in the increasing order of their acidity:
Propanol, propane, propanal (boiling point)
iii) Write the mechanism (using curved arrow notation) of the following reaction:
Solution :
i) B2H6, H2O, H2O2 and OH–
ii) Propane < Propanal < Propanol
iii)

207
4. What type of isomerism does exist between the following pairs of compounds.
a) Pentan - 1 - ol and Pentan - 2 - ol
b) Pentan - 1 - ol and 3 - Methylbutan - 1 - ol
c) Butan - 1- ol and Diethyl ether
Solution :
a)
b)
c)
5. Prepare Pentan - 1 - ol from
a) 1 - Bromopropane b) Pent - 1- ene
Solution :
Br
|
a) CH − CH − CH  Mg
→ CH 3 − CH 2 − CH 2 MgBr
3 2 2 ether
1 − bromopropane
+
CH 3 − CH 2 − CH 2 − CH 2 − CH 2 ←
H3 O
 CH 3 − CH 2 − CH 2 − CH 2 − CH 2
| |
OH O MgBr
b)

208
6. 3 - Phenylbut - 1 - ene on hydration in dil H2SO4 forms 2 - Phenylbutan - 2- ol instead of

3 - Phenyl butan - 2 - ol explain why?
Hydration gives an intermediate 2o - carbocation which undergoes a hydride shift to more stable
3o - carbocation.
7. Name the reagents used for the following conversions

i) Ethanol to Ethanoic acid
ii) Propan-2-ol to Propene
iii) Butan-2-one to Butan-2-ol
Solution :
+
i) CH 3 − CH 2 − OH →
H / KMnO
4
CH 3 − COOH
ii)
iii)

209
8. Alcohols react both as nucleophiles as well as electrophiles. Write one reaction of each type
and describe its mechanism.

Alcohols as nucleophiles
The bond between O – H is broken when alcohols react as nucleophiles.
Alcohols as electrophiles
The bond between C – O is broken when alcohols react as electrophiles. Protonated alcohols
react in this manner.
⊕
R − CH 2 H + → R − CH 2 OH 2
⊕
Br ⊙ + CH 2 − OH 2 → Br − CH 2 + H 2
| |
R R
9. A compound ‘A’ is optically active. On mild oxidation, it gives a compound ‘B’ but on
vigorous oxidation gives another compound ‘C’. C along with D is also formed from B by
reaction with iodine and alkali. Deduce the structures of A, B, C, D

210
10. How do you convert the following?

i) Isopropyl alcohol to tert-butyl alcohol
ii) n-Propyl alcohol to isopropyl alcohol
iii) Isopropyl alcohol to n-propyl alcohol
Solution :
i)
ii)
iii)
11. Write the mechanism of hydration of ethene to yield ethanol.

The mechanism of hydration of ethene to form ethanol involves three steps.
Step 1 :
Protonation of ethene to form carbocation by electrophilic attack of H3O+;

211
Step 2 :
Nucleophilic attack of water on carbocation :
Step 3 :
Deprotonation to form ethanol:
12. Classify the following as primary, secondary and tertiary alcohols :
i) ii) H2C = CH – CH2OH iii) CH3– CH2 – CH2 – OH
iv) v) vi)
Solution :
Primary alcohols : (i), (ii), (iii)
Secondary alcohols : (iv), (v)
Tertiary alcohols : (vi)

212
13. Write structures of the products of the following reactions :
i)
ii)
iii)
Solution
i)
ii)
iii)
14. Show how will you synthesize :

i) 1-Phenylethanol from a suitable alkene.
ii) Cyclohexylmethanol using an alkyl halide by an SN2 reaction.
iii) Pentan-1-ol using a suitable alkyl halide?
Solution
i) By acid-catalysed hydration of ethylbenzene (styrene), 1-phenylethanol can be synthesized.

213
ii) When chloromethylcyclohexane is treated with sodium hydroxide, cyclohexylmethanol is obtained.
iii) When 1-chloropentane is treated with NaOH, pentan-1-ol is produced.

CH3CH2CH2CH2CH2Cl + NaOH → CH3CH2CH2CH2CH2OH + NaCl
1-Chloropentane Pantan-l-ol
15. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place :
Give a mechanism for this reaction.

Solution :
The mechanism of the given reaction involves the following steps :
Step 1 : Protonation :
Step 2 : Formation of 2o carbocation by the elimination of a water molecule :
Step 3 : Re-arrangement by the hydride-ion shift
Step 4 : Nucleophilic attack :

214
16. Write the mechanism of acid catalysed dehydration of ethanol to yield ethene.
The mechanism of dehydration of ethanol involves the following steps :
Step 1 : Formation of protonated alcohol
Step 2 : Formation of carbocation : It is the slowest step and hence, the rate determining step to
the reaction.
Step 3 : Formation of ethene by elimination of a proton
The acid used in step 1 is released in step 3. To drive the equilibrium to the right, ethene is
removed as it is formed.
5 MARK QUESTIONS :
1. Name the following compounds according to IUPAC system
i) ii)
iii) iv)
v)
Solution :
i) 3-Chloromethyl-2-isopropylpentan-1-ol
ii) 2, 5-Dimethylhexane-1, 3-diol
iii) 3-Bromocyclohexanol
iv) Hex-1-en-3-ol
v) 2-Bromo-3-methylbut-2-en-1-ol
215
2. Give structures of the products you would expect when each of the following alcohol reacts with
a) HCl-ZnCl2 b) HBr c) SOCl2
i) Butan-1-ol
ii) 2-Methylbutan-2-ol
Solution :
a) i) CH3 - CH 2 - CH 2 - CH 2 - OH → No reaction

HCl-ZnCl 2
Butan -1- ol
Primary alcohols do not react appreciably with Lucas’ reagent (HCl-ZnCl2) at room temperature.
ii)
Tertiary alcohols react immediately with Lucas’ reagent.
CH 3CH 2 CH 2 CH 2 OH + HBr 

− H2O
→ CH 3CH 2 CH 2 CH 2 Br
b) i)
Butan -1- ol 1- Bromobutane
ii)
CH 3CH 2 CH 2CH 2OH + SOCl2 → CH 3CH 2CH 2CH 2 Cl + SO 2 + HCl

c) i)
Butan -1- ol 1- Chlorobutane
ii)

216
3. Write structures of the compounds whose IUPAC names are as follows :

i) 2-Methylbutan-2-ol vi) 2-Ethoxy-3-methylpentane
ii) 1-Phenylpropan-2-ol vii) Cyclohexylmethanol
iii) 3, 5-Dimethylhexane -1,3, 5-triol viii) 3-Cyclohexylpentan-3-ol
iv) 2, 3-Diethylphenol ix) Cyclopent-3-en-1-ol
v) 1 - Ethoxypropane x) 4-Chloro-3-ethylbutan-1-ol
Solution :
vii)
i)
ii)
viii)
iii)
ix)
iv)
x)
v) CH3CH 2OCH 2CH 2CH3
vi)
4. Draw the structures of all isomeric alcohols of molecular formula C5H12O and give their IUPAC
names and Classify the isomers of alcohols as primary, secondary and tertiary alcohols.
The structures of all isomeric alcohols of molecular formula, C5H12O are shown below :
a) CH3 - CH 2 - CH 2 - CH 2 - CH 2 − OH CH3
Pentan-1-ol (1o) |
d)
CH3 − C − CH2 − OH
b) CH 3 - CH 2 - CH - CH 2 - OH |
| CH3
CH 3
2, 2-Dimethylpropan-1-ol (1o)
2-Methylbutan-1-ol (1o)
OH
c) CH3 - CH - CH 2 - CH 2 - OH |
| e) CH - CH - CH - CH - CH
3 2 2 3
CH3
Pentan-2-ol (2o)
3-Methylbutan-1-ol (1o)
217
CH3 OH OH
| | |
f)
CH3 - CH - CH - CH 3 h)
CH3 - CH 2 - C - CH 3
|
3- Methylbutan-2-ol (2o) CH 3
OH 2-Methylbutan-2-ol(3o)
g) |
CH3 - CH 2 - CH - CH 2 - CH3
Pentan-3-ol (2o)
[PHENOLS]
1 MARK QUESTIONS :
1. Phenol is an acid but does not react with sodium bicarbonate solution. Why?
Phenol is a weaker acid than carbonic acid (H2CO3) and hence does not liberate CO2 from
sodium bicarbonate.
2. How will you distinguish between 1- phenyl ethanol and 2- phenyl ethanol?
Can be distinguished by haloform test. (II) gives haloform test but not (I)
3. Name the phenol with MF C7H8O which on treatment with Br2 water readily gives a
precipitate of C7H5OBr3
3-Methyl phenol 2, 4, 6-Tribromo-3-methyl phenol

218
4. Phenol is more acidic than Ethyl alcohol. Why?
Phenol > water > ethanol.
Phenoxide ion which is stabilized by resonance, where as ethoxide ion C2H5O- is destabilized by
+I effect
5. Alcohols react with halogen acids (or) phosphorous halides to form haloalkanes but phenol
does not form halobenzene. Explain.
In phenol due to resonance C – X bond aquires partial double character which is difficult to
break
6. Why phenol has higher boiling point than toluene.

Phenol has inter molecular H – bond. So B.P is higher than toluene.
7. Write chemical reaction for the preparation of phenol from chlorobenzene.
8. Explain how does the −OH group attached to a carbon of benzene ring activate it towards
electrophilic substitution?
group is +M group. In OH group oxygen has lone pairs, & group donate lone pair
to benzene ring & increase e- density at ortho & para position of benzene ring.
9. Out of o-nitrophenol and o-cresol which is more acidic?

o – nitro phenol is more acidic because nitro group is – I & - M group.
Acidic nature α − I
α−M

219
10. What happens when benzene diazonium chloride is heated with water?
+ N2 + HCl
11. In Kolbe’s reaction, instead of phenol, phenoxide ion is treated with CO2. Why?
Phenoxide ion is more reactive towards electrophilic aromatic substitution reactions.
12. Dipole moment of phenol is smaller than that of methanol. Why?
Sp2 carbon is more electronegative than Sp3 carbon
13. Arrange the following compounds in the increasing order of their acid strengths:
4-nitrophenol, phenol, 2,4,6-trinitrophenol
Phenol < 4-nitrophenol < 2,4,6-trinitrophenol
14. o–nitrophenol is more acidic than o – methoxyphenol. Why?

Acidic nature α - M
α-I
- NO2 group is – M & - I
15. Explain why is OH group in phenols more- strongly held as compared to OH group in
alcohols.
In phenol oxygen atom is attached to sp2 hybridised carbon atom while in alcohol it is attached
to sp3 hybridised carbon atom. The bond formed between oxygen and sp2 hybridised carbon
atom is more strongly held then that formed between oxygen and sp3 hybridised carbon atom.
16. Explain why nucleophilic substitution reactions are not very common in phenols.
Due to resonance, C – O bond in phenol attains partial double bond character.

220
17. 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?
Phenol in more easily nitrated than benzene, because phenol has activating –OH group.
18. How is toluene obtained from phenol?
19. Out of o-nitrophenol and p-nitrophenol, which is more volatile? Explain.

Ortho nitrophenol, is more volatile in steam due to chelation. Intramolecular hydrogen bonding
in o-nitrophenol and intermolecular hydrogen bonding in p-nitrophenol.
2 MARK QUESTIONS :
1. Arrange: water, ethanol and phenol in increasing order of acidity and give reason for your
answer.
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 increases 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.
2. Account for the following:

(i) Phenol does not react with NaHCO3 whereas carboxylic acids react.
(ii) Phenol is more easily nitrated than benzene.
Solution :
Such acid–base reaction takes place only if the acid formed is weaker than the reacting acid.
In other words, phenol is not a strong enough acid to react with NaHCO3.

221
+
ii) Nitration involves attack of electrophile nitronium ion  N O 2  on benzene ring. Due to +R
 
effect of —OH group electron density on benzene increases. Therefore, phenol is more easily
nitrated as compared to benzene.
3. How will you synthesis phenol from aniline?
4. Give the equations of reactions for the preparation of phenol from Cumene.
5. Give two reactions that show the acidic nature of phenol.
6. When phenol is treated with bromine water, white ppt. is formed. Give the structure and name
of the compound formed.

222
2, 4, 6- tribromophenol
7. Write steps to carry out the conversion of phenol to aspirin.

Step – 1
Step – 2
Step – 3
8. Answer the following questions:

(i) Dipole moment of phenol is smaller than that of methanol. Why?
(ii) In Kolbe’s reaction, instead of phenol, phenoxide ion is treated with carbon dioxide. Why?
Solution :
i) 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 electron-releasing effect of —CH3
group.
ii) Phenoxide ion is more reactive than phenol towards electrophilic aromatic substitution
and hence undergoes electrophilic substitution with carbon dioxide which is a weak
electrophile.

223
9. Explain why Lewis acid is not required in bromination of phenol?
During bromination of any non – polar substance like benzene, lewis acid is used to polarize the
attacking electrophile Br2. But in case of highly polar phenol molecule, the oxygen atom present
in the phenol molecule itself polarizes the incoming electrophite Br2 to form ions. So in case of
phenol no additional Lewis acid is required.
10. How will you know whether a given – OH group is alcoholic (or) phenolic in nature?
Phenolic OH group gives blue or violet colouration with neutral FeCl3, while the alcoholic OH
group does not give positive dye test.
11. The carbon-oxygen bond in phenol is slightly stronger than that in methanol. Why?
This is due to the fact that
In phenol, conjugation of unshared electron pair over oxygen with aromatic ring results in partial
double bond character in carbon-oxygen bond.
In phenol, oxygen is attached to a sp2 hybridised carbon atom while in methanol, it is attached to
a sp3 hyrbridised carbon atom. The bond formed between oxygen and sp2 hybridised carbon is
more stable than that formed between oxygen and sp3 hybridised carbon.
12. What happens when

(i) Phenol reacts with Conc. HNO3?
(ii) Ethyl chloride reacts with NaOC2H5?
Write the chemical equations involved in the above reactions.
Solution :
13. How would you obtain picric acid (2, 4, 6-trinitrophenol) from phenol?

224
14. How would you obtain Benzoquinone from phenol?
3 MARK QUESTIONS :
1. Explain the following named reactions with suitable equations.
i) Reimer-Tiemann reaction ii) Kolbe’s reaction
i) Reimer-Tiemann reaction
Treatment of phenol with chloroform in the presence of sodium hydroxide followed by
hydrolysis of resulting product gives o-hydroxybenzaldehyde (salicylaldehyde) as a major
product.
ii) Kolbe’s reaction

When sodium phenoxide is heated with CO2 at 400K under a pressure of 4 – 7 atm, the
resulting product on acidification yields salicylic acid.

225
2. Give equations of the following reactions:
i) Bromine in CS2 with phenol.
ii) Dilute HNO3 with phenol.
iii) Treating phenol with chloroform in presence of aqueous NaOH.
Solution :
i)
ii)
iii)
Minor
3. Arrange the following compounds in increasing order of acidity and give the suitable
explanation
phenol, o-nitrophenol, o-cresol
Solution :
o – nitrophenol > phenol > o – cresol.
Acidic nature α - M, - I
1
α
+ M, + I

226
(i) Phenol to benzyl alcohol
(ii) Phenol to m-bromophenol
(iii) Phenol to aspirin.
5 MARK QUESTIONS :
1. An aromatic compound ‘A’ on treatment with CHCl3/KOH gives two compounds ‘B’ and ‘C’.
Both B and C give the same product ‘D’ when distilled with zinc dust. Oxidation of D gives E
having molecular formula C7H6O2. The sodium salt of E on heating with sodalime gives F
which may also be obtained by distilling A with zinc dust. Identify A to F.
Solution :

227
[ETHERS]
1 MARK QUESTIONS :
1. Why are higher ethers insoluble in water?
Due to bigger size of the alkyl groups, the oxygen atom in ethers fails to form intermolecular
H – bonds with water.
2. Write the structure of isopentyl phenyl ether.

CH 3
|
CH 3 − CH − CH 2 − CH 2 − O −
3. Butan – 1 – ol has a higher boiling point than diethylether. Why?

Butan – 1 – ol has intermolecular H – bond. So more B.P
4. Why the dipole moment of ether is less than that of water.

Due to less electro – negativity difference between carbon & oxygen of (C - O) compared to
that of oxygen & hydrogen of (O - H) bond.
So C – O bond is less polar than O – H bond.

228
CH 3
|
5. Write the major products in the following reaction. CH 3 − C − O − CH 3 + HI 
→
|
CH 3
CH 3 CH 3
| |
CH 3 − C − O − CH 3 + HI 
→ CH 3 − C − I + CH 3OH
| |
CH 3 CH 3
6. Diethyl ether does not react with sodium. Why?

Diethyl ether does not have acidic hydrogen attached to oxygen.
7. Write the chemical equations involved in Nitration of anisole.
8. (CH3)3C – O – CH3 on reaction with HI gives (CH3)3 C – I and CH3 – OH as the main
products and not (CH3)3 C – OH and CH3 – I. Explain why?
CH 3
|
CH 3 − C ⊕ is more stable carbocation
|
CH 3
2 MARK QUESTIONS :
1. Write structural formula and IUPAC name of methyl tert- butyl ether.
CH 3
|
CH 3 − O − C − CH 3 2- methoxy – 2- methyl propane
|
CH 3
229
2. Why are boiling points of ethers lower than those of alcohols of comparable molecular
masses?
Alcohols have intermolecular H – bond but ethers do not have.
3. Explain Williamson’s ether synthesis.

Alkyl halide reacts with sodium alkoxide to form ether is known as Williamson’s synthesis.
RO− Na + + R1 − Cl 
→ R − O − R1 + NaCl it proceeds via SN2.
4. Anisole reacts with HI to give phenol and methyl iodide and not iodobenzene and methyl
alcohol. Why?
highly unstable is more stable.
5. How is 1 – propoxypropane synthesised from propan- 1 – ol?

+
2CH3CH2CH2 − OH 
H
414K
→ CH3CH2 − CH2 − O − CH2CH2CH3 + H2O
+
Mech : CH 3 − CH 2 − CH 2 − −H 
H
→ CH3 − CH2CH2 − −H
CH 3 − CH 2CH 2 − + CH 3 − CH 2 − CH 2 − 
→CH3CH2CH2 − − CH 2 CH 2 CH 3 + H 2O
−CH 2 CH 2 CH 3 
H2 O
→ CH 3CH 2 CH 2 − O − CH 2 CH 2 CH 3
CH 3CH 2CH 2 − +H+
1 − propoxy propane
6. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable

method. Give reason.
The formation of ethers by dehydration of alcohol is a bimolecular reaction (SN2) involving the
attack of an alcohol molecule on a protonated alcohol molecule. In this method, the alkyl group
should be unhindered. In case of secondary or tertiary alcohols, the alkyl group is hindered. As a
result, elimination dominates substitution. Hence, in place of ethers, alkenes are formed.

230
7. Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Ethanol undergoes intermolecular H-bonding due to the presence of a hydrogen attached to the
electronegative oxygen atom. As a result, ethanol exists as associated molecules.
Consequently, a large amount of energy is required to break these hydrogen bonds. Therefore,
the boiling point of ethanol is higher than that of methoxymethane which does not form H-
bonds.
8. Illustrate with examples the limitations of Williamson synthesis for the preparation of certain
type of ethers.
i) Williamson’s synthesis cannot be employed for tertiary alkyl halides as they yield alkenes
instead of ethers. The reaction of CH3ONa with (CH3)3C–Br gives exclusively
2-methylpropene.
ii) Aryl halides and vinyl halides cannot be used as substrates because of their low reactivity in
nucleophilic substitution.
3 MARK QUESTIONS :
1. Write the mechanism of the following reaction:
+ H2 O
The formation of ether is a nucleophilic bimolecular reaction (SN2) involving the attack of
alcohol molecule on protonated alcohol as shown below:

231
2. Give the major products that are formed by heating each of the following ethers with HI.
Solution :
3. Write the products of the following reactions:
Solution :

232
4. Write the IUPAC names of the following compounds.
i) C6H5 – O – C2H5
ii) CH 3 − CH 2 − O − CH − CH 2CH 3
|
CH 3
Solution :
i) Ethoxy benzene
ii) 2 – Ethyoxybutane
5. Write the structures of the compounds whose IUPAC names are as follows:
i) 1 – Ethoxypropane
ii) 2 – Ethoxy -3 – methylpentane
iii) Cyclohexylmethanol
Solution :
CH 3
CH 2 − CH 2 − CH 3 |
i) | ii) H3C − HC − HC − H 2C − CH3 iii)
O − CH 2CH 3 |
O − CH 2 CH 3
6. Write the names of reagents and equations for the preparation of the following ethers by
Williamson’s synthesis:
i) 2- Methyl – 2 – methoxypropane
ii) 1 – Methoxyethane
Solution :
CH 3 CH 3
| |
i) CH 3 − C − ONa + CH 3 − X 
→ CH 3 − C − O − CH 3 + NaX
| |
CH 3 CH 3
ii) CH3 − CH2 − ONa + CH3 − X 

→CH3 − CH2 − O − CH3

233
7. Give IUPAC names of the following ethers :
C2 H 5 OCH 2 - CH - CH 3
i) | v)
CH 3
ii) CH3OCH2CH2Cl
iii) O2N – C6H4 – OCH3(p) vi)
iv) CH3CH2CH2OCH3
Solution :
i) 1-Ethoxy-2-methylpropane iv) 1-Methoxypropane
ii) 1-Chloro-2-methoxyethane v) 4-Ethoxy-1,1-dimethylcyclohexane
iii) 4-Nitroanisole vi) Ethoxybenzene
8. Write the mechanism of the reaction of HI with methoxymethane.

The mechanism of the reaction of HI with methoxymethane involves the following steps :
Step 1 : Protonation of methoxymethane
Step 2 : Nucleophilic attack of I– :
Step 3 :
When HI is in excess and the reaction is carried out at a high temperature, the methanol formed
in the second step reacts with another HI molecule and gets converted to methyl iodide.

234
9. Predict the products of the following reactions :
Solution :
5 MARK QUESTIONS :
1. Phenols undergo electrophilic substitution reactions readily due to the strong activating effect
of OH group attached to the benzene ring. Since, the OH group increases the electron density
more at o- and p- positions therefore OH group is ortho, para-directing. Reimer-Tiemann
reaction is one of the examples of electrophilic substitution reaction. Riemer-Tiemann
reaction introduces an aldehyde group on the aromatic ring of phenol, ortho to the hydroxyl
group. This a general method for the synthesis of substituted salicyladehydes. In this
reaction, treatment of phenol with chloroform in presence of aqueous sodium or potassium
hydroxide at 340K followed by hydrolysis of the reacting product gives
2-hydroxybenzaldehyde as the major product.

235
i) What is the electrophile used in Reimer-Tiemann reaction?
ii) Draw the structure of the intermediate in the following reaction
iii) Write the IUPAC name of the product formed in the equation given in above question
iv) Which is more reactive, phenol or benzene towards electrophilic substitution?
v) What happens when carbontetrachloride is used in the reaction instead of chloroform?
Solution :
i) :CCl2 dichloro carbene
ii)
iii) 2 – Hydroxyl – 5 – methylbenzaldehyde
iv) Phenol due to +M effect of – OH group
v) is formed instead of

236
2. Williamson’s synthesis is one of the best methods for the preparation of ethers. It involves the
treatment of an alkylhalide with a suitable sodium alkoxide. Williamson’s synthesis involves
nucleophilic substitution of the halogen atom of an alkylhalide by an alkoxide group as
shown below.
⊙ ⊕
R − O Na + R '− X → R − O − R '+ Na X
When alkyl halide used in the reaction is primary, Williamson’s synthesis proceeds via SN2
mechanism leading to the formation of an ether. This method is a versatile method for the
synthesis of both symmetrical and unsymmetrical ethers.
i) Why is Williamson’s synthesis not applicable when the alkyl halide used is tertiary?
ii) How would you obtain allyl phenyl ether?
iii) What happens when benzyl ethylether reacts with HI?
iv) Name the alkyl halide and sodium alkoxide used to synthesise tert-butyl ethylether.
v) (CH3)3C – O – CH3 on reaction with HI gives (CH3)3C – I and CH3 – OH as the main
products but not (CH3)3 C – OH and CH3 – I. Give reason.
Solution :
i) Williamson’s synthesis is an SN2 reaction.
For SN2 1° > 2° > 3°
ii) + CH2 = CH − CH2 − Cl 

→
iii)
CH 3
|
iv) CH − C − ONa & C H − Cl
3 2 5
|
CH 3
CH 3
|
v) CH 3 − C ⊕ is more stable.
|
CH 3

237
3. Write the names of reactants and equations for the preparation of the following ethers by
Williamson’s synthesis :
i) 1-Propoxypropane
ii) Ethoxybenzene
iii) 2.Methoxy-2-methylpropane
iv) 1-Methoxyethane
Solution :
CH 3CH 2 CH 2O − Na + + CH 3CH 2 CH 2 Br → C2 H 5CH 2 - O - CH 2 C2 H 5 + NaBr
i)
Sodiumpropoxide 1- Bromopropane 1- Propoxypropane
ii)
iii)
CH 3CH 2 - O − Na + + CH 3 - Br → CH 3CH 2 - O - CH 3 + NaBr

iv)
Sodium ethoxide Bromopropane 1- Methoxyethane
4. Write equations of the following reactions:

i) Friedel-Crafts reaction-alkylation of anisole.
ii) Nitration of anisole.
iii) Bromination of anisole in ethanoic acid medium
iv) Friedel-Craft's acetylation of anisole.
Solution :
i)

238
ii)
iii)
iv)
5. Predict the products of the following reactions :

i) CH3 - CH 2 - CH 2 - O - CH3 + HBr →
ii)
iii)
iv) ( CH3 )3 C - OC2 H5 →

HI
Solution :
i) CH3 - CH 2 - CH 2 - O - CH 3 + HBr → CH 3 - CH 2 - CH 2 - OH + CH 3 - Br
ii)

239
iii)
( CH 3 )3 C - OC2 H 5 →
HI
( CH 3 )3 C - I + C 2 H 5OH
iv)
tert - Butyl ethyl ether tert - Butyliodide Ethanol
6. Write IUPAC names of the following compounds :

CH 3
|
i) CH 3 - CH - CH - C - CH3
| | |
CH3 OH CH 3 vii)
H 3C - CH - CH 2 - CH - CH - CH 2 − CH3
ii) | | |
OH OH C2H 5
CH3 - CH - CH - CH3
iii) | |
OH OH
viii)
HO - CH 2 - CH - CH 2 - OH
iv) |
OH
CH3 ix) CH 3 - CH 2 - O - CH 2 - CH - CH 3
|
OH CH 3
v)
x) C6H5 – O – C2H5
xi) C6H5 – O – C7H15
xii) CH 3 - CH 2 - O - CH - CH 2 - CH 3
|
CH 3
vi)
Solution :
i) 2, 2, 4-Timethylpentan-3-ol vii) 2, 5-Dimethylphenol
ii) 5-Ethylheptane-2, 4-diol viii) 2, 6-Dimethylphenol
iii) Butane-2,3-dio1 ix) 1-Ethoxy-2-methyl propane
iv) Propane-1, 2, 3-triol x) Ethoxybenzene
v) 2-Methylphenol xi) 1-Phenoxyheptane
vi) 4-Methylphenol xii) 2-Ethoxybutane

7. Give the major products that are formed by heating each of the following ethers with HI.
Solution :
i)
i)
ii)
ii)
iii)
iii)
8. Write the structures of the compounds whose IUPAC names are as follows:
i) 2-Methylbutan-2-ol ii) 1-Phenylpropan-2-ol
iii) 3, 5-Dimethylhexane-1, 3, 5-triol iv) 2, 3-Diethylphenol
v) 1-Ethoxypropane vi) 2-Ethoxy-3-methylpentane
vii) Cyclohexylmethanol viii) 3-Cyclohexylpentan-3-ol
ix) Cyclopent-3-en-1-ol x) 4-Chloro-3-ethylbutan-1-ol
Solution :
Hreen Qark, Okl VOLUME - I

241
CASE STUDY QUESTIONS :
1. Phenols undergo electrophilic substitution reactions readily due to the strong activating effect
of OH group attached to the benzene ring. Since, the OH group increases the electron density
more at o- and p-positions, the OH group is ortho and para-directing. Reimer-Tiemann
reaction is one of the examples of electrophilic substitution reaction. Riemer-Tiemann
reaction introduces an aldehyde group on the aromatic ring of phenol, ortho to the hydroxyl
group. This is a general method for the synthesis of substituted salicylaldehydes. In this
reaction, treatment of phenol with chloroform in presence of aqueous sodium or potassium
hydroxide at 340 K followed by hydrolysis of the reacting product gives 2-
hydroxybenzaldehyde as the major product.
i) What is the electrophile used in Reimer-Tiemann reaction?

:CCl2
ii) Draw the structure of the intermediate in the following reaction:
iii) Write the IUPAC name of the product formed in the equation given in above question.
2-hydroxy-5-methylbenzaldehyde
iv) Which is more reactive, phenol or benzene towards electrophilic substitution?
Phenol is more reactive than benzene towards electrophilic substitution reaction because
in case of phenol, OH group increases the electron density at ortho and para positions.
v) What happens when carbon tetrachloride is used in the reaction instead of chloroform?
Salicylic acid is formed as the major product.

242
2. Williamson’s synthesis is one of the best methods for the preparation of ethers. It involves the
treatment of an alkyl halide with a suitable sodium alkoxide. Williamson’s synthesis involves
nucleophilic substitution of the halogen atom of an alkyl halide by an alkoxide group as
shown below:
When alkyl halide used in the reaction is primary, Williamson’s synthesis proceeds via SN2
mechanism leading to the formation of an ether. This method is a versatile method for the
synthesis of both symmetrical and unsymmetrical ethers.
i) Why is Williamson’s synthesis not applicable when the alkyl halide used is tertiary?
This is because 3° alkyl halides are highly susceptible to dehydrohalogenation in the
presence of sodium alkoxides and elimination reaction occurs.
ii) How would you obtain allyl phenyl ether?
Allyl phenyl ether can be obtained by heating allyl halide and sodium phenoxide.
iii) What happens when benzyl ethyl ether reacts with HI?
Benzyl iodide and ethyl alcohol will be formed after the reaction of benzyl ethyl ether
with HI.
iv) Name the alkyl halide and sodium alkoxide used to synthesise tert-butyl ethyl ether.
Ethyl bromide and sodium tert-butoxide.
v) (CH3)3C–O–CH3 on reaction with HI gives (CH3)3C–I and CH3–OH as the main
products and not (CH3)3C–OH and CH3–I. Give reason.
The reaction between (CH3)3COCH3 and HI follows SN1 mechanism. For an SN1 reaction,
the formation of product is controlled by stability of the carbocation formed in the slowest
⊕
step. Since tert-butyl carbonium ion (CH3)3 C formed after the cleavage of C–O bond in
⊕
the slowest step is more stable than methyl carbonium ion ( C H3) therefore (CH3)3C–I and
CH3OH are the main products.

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INTERNATIONAL SR.SEC.

4 HALO ALKANES & HALO ARENES 139

5 ALCOHOLS, PHENOLS & ETHERS 199

[Expressing concentration of Solutions]

Hreen Qark, Okl Q & A [VOLUME - I]

2. Define Mole fraction?

5. Define Mass percentage?

Hreen Qark, Okl Q & A [VOLUME - I]

= 2.45 × 10-8 mol L-1.

Hreen Qark, Okl Q & A [VOLUME - I]

Mass of acrtonitrile = 450 g

Volume solution = 250 mL = 0.25 L

Molar mass solute = (12 x 6) + (1 x 5) + (12) + (16 x 2) + (1)

Mass of solute = ( 0.15 x 122 x 0.25) g = 4.575 g

Hreen Qark, Okl Q & A [VOLUME - I]

2. Calculate the molarity of 30 g of Co(NO3)26H2O in 4.3 L of solution

the mass percentage of the resulting solution.

4. Nalorphene (C19H21NO3), similar to morphine, is used to combat withdrawal symptoms in narcotic

solution required for the above dose.

m = 1.5 x 10-3 m or 1.5 x 10-3 mol kg-1

Mass of solute = 1.5 x 10-3 g or 1.5 mg

Molar mass of solute

(C19H21NO3) = (12 x 19) + (1 x 21) + (14) + (16 x 3)

Hreen Qark, Okl Q & A [VOLUME - I]

Hreen Qark, Okl Q & A [VOLUME - I]

Hreen Qark, Okl Q & A [VOLUME - I]

Hreen Qark, Okl Q & A [VOLUME - I]

2. Define Henry’s law.

= 178 × 10-5 (approximately)

Hreen Qark, Okl Q & A [VOLUME - I]

4. Based on solute-solvent interactions, arrange the following in order of increasing solubility in n-

Hreen Qark, Okl Q & A [VOLUME - I]

Hreen Qark, Okl Q & A [VOLUME - I]

According to Henry’s law :P

Hreen Qark, Okl Q & A [VOLUME - I]

Partial pressure of N2 ( PN 2 ) = (10 atm ) x

[Vapour pressure of liquid solutions]

Hreen Qark, Okl Q & A [VOLUME - I]

2. Define non-ideal solutions and give any two examples.

2. Define minimum boiling azeotropes and give one example.

3. Write two differences between ideal solution and non-ideal solutions.

Hreen Qark, Okl Q & A [VOLUME - I]

Hreen Qark, Okl Q & A [VOLUME - I]

Raoult’s law (given in figure).

Hreen Qark, Okl Q & A [VOLUME - I]

Mole fraction of solute

Mole fraction water (xA) = 1- 0.0177= 0.9823

Ptotal = PA0 x A + PB0 (1 − x A )

Ptotal = PA0 x A + PB0 − PB0 x A

Ptotal = ( PA0 − PB0 ) x A + PB0

Hreen Qark, Okl Q & A [VOLUME - I]

⇒ 600 = (450 – 700)xA + 700

Hence, xB = 1-xA = 0.6

= 450 × 0.4 = 180 mm of Hg

Vapour pressure of heptane ( p10 ) = 105.2 kPa

Vapour pressure of octane ( p 02 ) = 46.8 kPa

Hreen Qark, Okl Q & A [VOLUME - I]

Hreen Qark, Okl Q & A [VOLUME - I]

Therefore, Mole fraction of benzene, xb

Number of moles of water