Academic Progress for every Student

Regular tests &

assignments

VEDANTU
IMPROVEMENT Report card with
PROMISE detailed analysis

VIP

Parent-teacher
meetings

Our Extraordinary Results 2022

5.2X
HIGHER

1414 869
CBSE 10 scored above
3.8X
Vedantu students
90% JEE Main
Vedantu students
scored above 99%ile
HIGHER
6.6X
HIGHER

1000+ 1500+
Vedantu students Vedantu students aced
NEET cleared NEET 2022 JEE Adv. JEE Advanced 2022

student scoring above 90%

SCAN CODE
to know more
about VIP
Published by
Vedantu Innovations Pvt. Ltd.
D. No. 1081, 3rd Floor, Vistar Arcade,
14th Main Rd, Sector 3, HSR Layout
Bangalore, Karnataka, India 560 102
www.vedantu.com

All rights reserved. No part of this book may be reproduced or utilized in any form or by any
means, electronic or mechanical, including photocopying, recording, or by any information
storage and retrieval system, without permission in writing from the publishers.
Notice: Vedantu is committed to serving students with the best resources and knowledge.
Bearing that in mind, we have obtained all the information in this book from sources regarded
as reliable, and taken utmost care in editing and printing this book. However, as authors and
publishers, we are not to be held responsible for unintentional mistakes that might have crept
in. Having stated that, errors (if any) brought to our notice shall be gratefully acknowledged
and rectified in upcoming editions.

Printed by
Sanjay Printers, U.P.
sanjayprinters1156@gmail.com
 How to use your
Tatva Practice Book

1
2. Hexagonal Packing
Hexagonal packing is more
efficient. Its coordination
number is 6 and voids in the
packing are smaller than square
packing. If we place another Scan the QR Code in each
layer on square packing then chapter’s theory section to
there are the following
view micro concept videos
related to the chapter, on
SCAN CODE the Vedantu app
Solid State

Exercise - 2:

2
Solve all types of
1. CsBr crystallizes in a body
centered cubic lattice. The edge
length of unit cell is 436.6 pm.
Given that the atomic mass of
Cs = 133u and Br = 80u, the
exercise questions density of CsBr is:
based on the latest JEE (JEE 2019)
pattern.
(a) 42.5 g/cm3 (b) 0.425 g/cm3
(c) 4.25 g/cm3 (d) 8.5 g/cm3

Answer Key

3
CHAPTER-1: SOLID STATE
For extra exam
Exercise-1: Basic Objective preparation content,
visit the Vedantu app.
Scan the QR code in the You can find previous
Answers Section to view years’ JEE papers with
detailed solutions for all solutions and detailed
exercise questions. analysis.
Founder’s Message
Dear Student,
I am delighted to present to you a Ready Reckoner and an amazing book to guide you for your
exams-‘TATVA’. Tatva—which means the ‘Core’ is fully aligned with the culture, the mission, and the
vision of Vedantu and therefore it gives me immense pleasure and joy to share this book with you. We
at Vedantu have always believed in revolutionizing the teaching and learning process and always
speedily progressed in the direction of bringing superior quality education and content to your table.
Tatva is a step forward in this direction. This book is your guide, your practice guru, and your
companion in moving towards your dreams. The book is a result of the consistent effort, diligence, and
research by our experienced team of subject experts and teachers.
This book has been customized with curated content to suit the needs of JEE aspirants like you and
guide you on the right path to cracking JEE and optimizing your efficiency. Tatva is a comprehensive
amalgamation of important concepts, theories, derivations, definitions, solved examples, concept
videos, practice questions, and important questions. We have ensured that high-quality content and
the right ingredients are in place in this booklet to help you climb up the success ladder.
A few guiding points to optimally use Tatva with a planned approach:
Tatva equips you with Theory, Concept Videos, and Solved examples to help you revise concepts,
mark your notes, walk you through the entire summary, and eventually makes you capable of
clearing all your conceptual doubts all by yourself.
We suggest revision of theory followed by practice of solved examples.
Practice relevant questions daily after finishing Vedantu lectures and session assignments. We
believe that a daily dose of Tatva will keep all your exam blues at bay.
Use the Tatva booklet to mark notes so that it always comes in handy for last-minute revision
sessions before your exams. Notes should include key points of theory, solved examples, and some
questions which you couldn't solve in the first attempt.
Exercise 1 and Exercise 2 of JEE Tatva deal with basic questions and those which can be asked or
already asked in JEE Main. Similarly, Exercise 3 and Exercise 4 deal with JEE Advanced level
questions. We recommend you solve basic JEE Main questions before moving to JEE Advanced
level questions.
Before wrapping up, the practice mantra: “Don't practice until you get it right. Practice until you
can't get it wrong.”

We strongly believe in you and your capabilities. So believe in yourself

because success is only one step away. Wishing that your talent shines
bright. All the very best!

Anand Prakash
Founder and Academic Head, Vedantu

Anand Prakash Sir has been a pioneer in producing Top Ranks in JEE/NEET
and Olympiads. He has personally taught and mentored AIR 1, 6, 7 (JEE
Advanced), AIR-1, 7, 9(AIIMS), and thousands of more students who have
successfully cleared these competitive exams in the last few years.
Credits
“Happiness lies in the joy of achievement
and the thrill of creative effort.”
—Franklin D. Roosevelt

Tatva is the brainchild of a group of creative Vedans who have strived tirelessly to weave success stories for you.
We extend our heartfelt gratitude to the superb team of Vedans who give wings to the vision of Vedantu,
starting with our leaders who have been guiding and encouraging us at every step of the way:
Vamsi Krishna Sir, Anand Prakash Sir and Pulkit Jain Sir

We thank our leaders for their insight and mentorship. They steered the project in the right direction and were
instrumental in making Tatva a reality:
Sahil Bhatia, Sudhanshu Jain, Shubam Gupta, Ajay Mittal, Arshad Shahid, Jaideep Sontakke

The managers who embodied every aspect of what Tatva aimed to accomplish and brought their ideas and
diligence to the table to execute this vision immaculately:
Harish Rao, Neha Surana, Charubak Chakrabarti, Prashant Palande

Chemistry Team
We truly appreciate all the Master Teachers of Vedantu whose relentless efforts helped us translate this vision
into reality. Our heartfelt gratitude to our creative content developers and the typesetting team, who have put
in their hard work, insight, and eagerness to nurture and execute Tatva into ‘your ready handbook’ and bring a
positive learning experience to you.
Teachers Subject Matter Experts
Lakshay Kathuria Sakshi Pahuja Seema Agarwal (TL)
Komal Puniani Rupali Bhadauria

Typesetting Team Graphic Designer

Amit Thakur Prajjwal Jain Moorthy R

We cannot thank the creative team enough. Their creative minds and contagious energy have added a visual
flair, truly making Tatva the treasure trove of knowledge that it is.
Kajal Nilanjan Chowdhury Rabin Jacob Mohit Kamboj
Kiran Gopal Balaji Sakamuri Thamam Mubarish Haritha Ranchith
Sarib Mohammad

We thank and appreciate the enthusiastic support provided by Arunima Kar, Savin Khandelwal, and Dipshi
Shetty.

The journey of bringing Tatva to life, from an idea to the book you are holding, would not have been possible
without the extensive support of our diligent Operations Team, our amazing Academic Team, our dedicated
team of Teachers, and our talented Tech Team.
 TABLE OF CONTENTS

SOLUTIONS

Theory ................................................................................................................................................ 8
Solved Examples ............................................................................................................................... 19

Exercise - 1 : Basic Objective Questions........................................................................................... 34

Exercise - 2 : Previous Year JEE MAINS Questions ........................................................................... 40

Exercise - 3 : Advanced Objective Questions ................................................................................. 47
Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 55
Answer Key ........................................................................................................................................ 297

SOLID STATE

Theory ................................................................................................................................................ 59

Solved Examples ............................................................................................................................... 74

Exercise - 1 : Basic Objective Questions........................................................................................... 85

Exercise - 2 : Previous Year JEE MAINS Questions ........................................................................... 90

Exercise - 3 : Advanced Objective Questions ................................................................................. 93

Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 100

Answer Key ........................................................................................................................................ 299

 GENERAL ORGANIC CHEMISTRY (Revision) & ISOMERISM

Theory ................................................................................................................................................... 103

Solved Examples ..................................................................................................................................... 130

Exercise - 1 : Basic Objective Questions.................................................................................................. 135

Exercise - 2 : Previous Year JEE MAINS Questions .................................................................................. 150

Exercise - 3 : Advanced Objective Questions ....................................................................................... 156

Exercise - 4 : Previous Year JEE Advanced Questions ....................................................................... ... 167

Answer Key .............................................................................................................................................. 301

ALKYL AND ARYL HALIDES

Theory ...................................................................................................................................................... 171

Solved Examples ..................................................................................................................................... 188

Exercise - 1 : Basic Objective Questions.................................................................................................. 196

Exercise - 2 : Previous Year JEE MAINS Questions................................................................................... 214

Exercise - 3 : Advanced Objective Questions ....................................................................................... 222

Exercise - 4 : Previous Year JEE Advanced Questions .......................................................................... 238

Answer Key .............................................................................................................................................. 303

ALCOHOLS, PHENOLS AND ETHERS

Theory ...................................................................................................................................................... 242

Solved Examples ..................................................................................................................................... 261

Exercise - 1 : Basic Objective Questions.................................................................................................. 268

Exercise - 2 : Previous Year JEE MAINS Questions .................................................................................. 274

Exercise - 3 : Advanced Objective Questions ....................................................................................... 284
Exercise - 4 : Previous Year JEE Advanced Questions ....................................................................... ... 291

Answer Key .............................................................................................................................................. 306

SOLUTIONS
 Chapter 01 9

SOLUTIONS

INTRODUCTION For example, common salt in water.

In normal life we rarely come across pure substances. Most of 1.1 Type of Solutions
these are mixtures containing two or more pure substances. Their Solutions which contain two components in it are called Binary
utility or importance in life depends on their composition. The air Solutions.
around us is a mixture of gases primarily oxygen and nitrogen; the Substances which are used to prepare a solution are called as
water we drink contains very small amounts of various salts Components.
dissolved in it. Our blood is a mixture of different components. The component that is present in the largest quantity is known
Alloys such as brass, bronze, stainless steel, etc. are also mixtures. as Solvent. Solvent determines the physical state in which
In this Unit, we will consider mostly liquid solutions and their solution exists.
properties. The other component present in lesser quantity in the solution is
termed as Solute.
1. SOLUTIONS
Each component may be solid, liquid or in gaseous state.
Definition :
A solution is a homogeneous mixture of two or more than two
components.
Type of Solution Solute Solvent Common Examples
Gas Gas Mixture of Oxygen and Nitrogen Gas
Gaseous Solutions Liquid Gas Chloroform mixed with nitrogen gas
Solid Gas Camphor in Nitrogen gas
Gas Liquid Oxygen dissolved in water
Liquid Solutions Liquid Liquid Ethanol dissolved in water
Solid Liquid Glucose dissolved in water
Gas Solid Solution of hydrogen in palladium
Solid Solutions Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold

1.2 Concentration term 2. Volume percentage (%v/v)

The amount of solute dissolved per unit solution or solvent is “It represents volume of a component in 100 mL of solution”
called Strength of solution. There are various methods of
measuring strength of a solution. : Vol. of component
Vol. % of a component = ×100
1. Mass Percentage (%w/w) Total vol. of solution

“It represents mass of a component present in 100 g of 3. Mass by volume percentage (%w/v)
solution”
“It represents mass of solute in grams present in 100 mL of
Mass % of a component = solution”

Mass of component in the sol. Mass of solute in g

 100 Mass by vol. percent = 100
Total Mass of Sol. Vol. of sol. in mL

SCAN CODE
SOLUTIONS
SOLUTIONS 10

4. Parts per Million (ppm) No. of Equivalents of solute

Normality 
As in the case of percentage, concentration in parts per Vol. of sol. in L
million can also be expressed as mass to mass, volume to
volume and mass to volume. Weight
No. of equivalents 
Parts per Million Equivalent weight (W / E)

No. of parts of the component M

 106 E (z is the valency factor)
Total no. of all the components of sol. z

Concentration in parts per million can be expressed as mass SOME IMPORTANT RELATIONSHIPS
to mass, volume to volume and mass to volume. Dilution Law :
5. Mole Fraction (x) If a solution is diluted by adding solvent to it, then the amount of
“It represents the moles of a solute present in one mole of solute remains constant and we can write:
solution” M1V1 = M2V2 and N1V1 = N2V2
Molarity and Normality :
No. of moles of the component
Mole fraction  Normality = z × Molarity
Total no. of moles all the components
(z = valency factor)
For example, in a binary mixture, if the number of moles of
A and B are nA and nB respectively, the mole fraction of NOTE
A will be Mass %, ppm, mole fraction and molality are independent
of temperature, whereas molarity & normality are a function
nA of temperature. This is because volume depends on
xA 
nA  nB temperature and the mass does not.
6. Molarity, (M) 2. VAPOUR PRESSURE OF LIQUID SOLUTION
“It represents moles of solute present in 1 L of solution”
2.1 Definition
Moles of solute
Molarity, M  Vapour pressure of a liquid/solution is the pressure exerted by
Vol. of sol. in L the vapours in equilibrium with the liquid/solution at a particular
Units of Molarity are mol/L also represented by ‘M’ or temperature.
‘Molar’. Vapour pressure  escaping tendency
“Density of a solution is mass of the solution per unit 2.2 Vapour pressure of liquid solutions and Raoult’s Law
volume” (Raoult’s law for volatile solutes)
Mass of sol. Raoult’s law states that for a solution of volatile liquids, the
Density, d   m/V partial vapour pressure of each component in the solution is
Vol. of sol.
directly proportional to its mole fraction.
7. Molality, m Consider a solution containing two volatile components 1 and 2
“It represents moles of solute present per kg of solvent” with mole fractions x1 and x2 respectively.
Suppose at a particular temperature, their partial vapour pressures
Moles of solute
Molality 
Mass of solvent in kg are p1 and p2 and the vapour pressure in pure state are p10 and p 02 .

Units of molality are mol/kg which is also represented by Thus, according to Raoult’s Law, for component 1
‘m’ or ‘molal’. p1  x1 and p1 = p10 x1
8. Normality, (N)
It represents no. of equivalents of solute present in 1 L of
solution.

SCAN CODE
SOLUTIONS
SOLUTIONS 11
Similarly, for component 2
2.3 Vapour pressure of solutions of solids in liquids and
p2  p x20 Raoult’s Law
2

According to Dalton’s law of partial pressure, the total pressure  Raoult’s law for non volatile solutes
(ptotal) over the solution phase in the container will be the sum of If a non-volatile solute is added to a solvent to give a solution,
the partial pressures of the components of the solution and is the number of solvent molecules escaping from the surface is
given as : correspondingly reduced, thus, the vapour pressure is also
reduced.
ptotal = p1 + p2
The decrease in the vapour pressure of solvent depends on the
Substituting the values of p1 and p2, we get
quantity of non-volatile solute present in the solution, irrespective
ptotal = x1 p10  x 2 p 02 of its nature.
Raoult’s law in its general form can be stated as, for any solution
 (1  x 2 ) p10  x 2 p 02 the partial vapour pressure of each volatile component in the
solution is directly proportional to its mole fraction.
 p10  (p 02  p10 ) x 2
In a binary solution, let us denote the solvent by 1 and solute by
2. When the solute is non-volatile, only the solvent molecules
are present in vapour phase and contribute to vapour pressure.
Let p1 be the vapour pressure of the solvent, x1 be its mole

fraction, p10 be its vapour pressure in the pure state. Then

according to Raoult’s law

p1  x1 and p1 = x1 p10 = ptotal

The plot of vapour pressure and mole fraction of an ideal solution

at constant temperature. The dashed line I and II represent the
partial pressure of the components. It can be seen from the plot
that p1 and p2 are directly proportional to x1 and x2, respectively.
The total vapour pressure is given by line marked III in the
figure
Mole fraction in vapour phase
If a solution obeys Raoult’s law for all concentrations,
If y1 and y2 are the mole fractions of the components 1 and 2
its vapour pressure would vary linearly from zero to the
respectively in the vapour phase then, using Dalton’s law of vapour pressure of the pure solvent
partial pressures:
2.4 Ideal and Non-ideal solutions
p1  y1p total Ideal solutions :
p 2  y 2 p total An ideal solution is the solution in which each component obeys
Raoult’s law under all conditions of temperatures and
In general
concentrations.
pi  yi p total Properties of Ideal solutions :
 HMIXING = 0
 VMIXING = 0

SCAN CODE
SOLUTIONS
SOLUTIONS 12
 Intermolecular attractive forces between the A-A and B-B
are nearly equal to those between A-B.
Eg. solution of benzene and toluene,
solution of n-hexane and n-heptane
Non – ideal solutions :
When a solution does not obey Raoult’s law over the entire
range of concentration, then it is called non-ideal solution.
Solutions showing positive deviation from Raoult’s Law :
 Solvent-Solute(A-B) type of force is weaker than Solute-
Solute(B-B) & Solvent-Solvent(A-A) forces.
 The vapour pressure is higher than predicted by the law.
 HMIXING > 0 Pressure composition curves for solution showing negative
deviation
 VMIXING > 0
Eg. ethanol and acetone, carbon disulphide and acetone 3. CONCEPT OF BOILING

a. Azeotropes
Azeotropes are binary mixtures having the same composition in
liquid and vapour phase and boil at a constant temperature.
Minimum boiling azeotrope :
The solutions which show a large positive deviation from Raoult’s
law form minimum boiling azeotrope at a specific composition.
For example, ethanol-water mixture containing approximately 95%
of ethanol forms an azeotrope with boiling point 351.15 K.

Pressure composition curve for solution

showing positive deviation
Solutions showing negative deviations from Raoult’s law :
 Solvent-Solute(A-B) type of force is stronger than the other
two.
 The vapour pressure is lower than predicted by the law Boiling temperature - composition Diagram for
 HMIXING < 0 solutions showing large positive deviations

 VMIXING< 0 (Minimum boiling azeotrope)

For example,phenol and aniline, chloroform and acetone etc Maximum boiling azeotrope:

The solutions that show large negative deviation from

Raoult’s law form maximum boiling azeotrope at a specific
composition. Nitric acid and water mixture containing 68%
nitric acid forms an azeotrope with a boiling point of 393.5 K.

SCAN CODE
SOLUTIONS
SOLUTIONS 13

Here K H is the Henry’s law constant.

Characteristics of KH:

 K H is a function of the nature of the gas.

 Higher the value of K H at a given pressure, the lower is the

solubility of the gas in the liquid.
 KH values increase with increase of temperature indicating
that the solubility of gases increases with decrease of
temperature.

Boiling temperature - composition Diagram for Applications of Henry’s law :

solutions showing large negative deviations 1. In the production of carbonated beverages.
(Maximum boiling azeotrope)
2. In the deep sea diving.
4. SOLUBILITY 3. For climbers or people at high altitudes.
Raoult’s Law as a special case of Henry’s Law :
4.1 Solubility of a solid in liquid
According to Raoult’s law,
Solubility of a substance is its maximum amount that can be
dissolved in a specified amount of solvent. pi = xi p i0

Factors affecting the solubility of a solid in liquid: In the solution of a gas in a liquid, one of the components is so
1. Nature of solute and solvent: volatile that it exists as a gas. Its solubility according to Henry’s
law,
Like dissolves like. For example, While sodium chloride
and sugar dissolve readily in water, naphthalene and p  K H x.
anthracene do not. On the other hand, naphthalene and
Thus, Raoult’s law becomes a special case of Henry’s law in
anthracene dissolve readily in benzene but sodium chloride
and sugar do not. which K H becomes equal to p i0 .

2. Temperature: 5. COLLIGATIVE PROPERTIES

In a nearly saturated solution,
The properties that depend on the number of solute particles
If (solH > 0), the solubility increases with rise in temperature
irrespective of their nature relative to the total number of particles
and If (solH < 0) the solubility decreases with rise in present in the solution are called colligative properties.
temperature.
There are four colligative properties:
3. Effect of pressure :
Does not have any significant effect as solids and liquids 1. Relative Lowering of vapour Pressure
are highly incompressible.
2. Elevation in Boiling Point
4.2 Henry’s law
3. Depression in freezing point
Henry’s law states that at a constant temperature, the solubility
of a gas in a liquid is directly proportional to the pressure of the 4. Osmotic pressure
gas.
5.1 Relative Lowering of vapour Pressure
The most commonly used form of Henry’s law states that “the
partial pressure of the gas in vapour phase (p) is proportional to When a non-volatile solute is added to a solvent, the vapour
the mole fraction of the gas (x) in the solution”. This is expressed pressure decreases.
as:
The lowering of vapour pressure w.r.t. the vapour pressure of
p  KH x the pure solvent is called “Relative lowering in vapour
pressure”.

SCAN CODE
SOLUTIONS
SOLUTIONS 14
According to Raoult’s Law :
K b is called Boiling Point Elevation Constant or Molal Elevation
p1  x1 p 0
1 Constant (Ebullioscopic Constant).
The reduction in the vapour pressure of solvent (p1) is given Calculation of molar mass of solute :
as:
w 2 / M2 1000  w 2
m 
p1  p  p1  p  p x1  p (1  x1 )
0
1
0
1
0
1
0
1
w1 /1000 M 2  w1

Knowing that x2 = 1 – x1, equation reduces to Substituting the value of molality in equation we get

p1  x 2 p10 K b 1000  w 2

Tb 
Equation can be wirtten as M 2  w1

p1 p10  p1 1000  w 2  K b

  x2 M2 
p10 p10 Tb  w1

The expression on the left hand side of the equation as mentioned Kb : It is defined as the elevation in boiling point when the molality
earlier is called relative lowering of vapour pressure and is equal of the solution is unity.
to the mole fraction of the solute. The above equation can be
The unit of Kb is K kg mol–1
written as :
Determination of Kb :
p10 - p1 n2  n2 
0
=  since x 2 =  R  M1  Tb2
p1 n1 +n 2  n1 +n 2  Kb 
1000   vap H
Here n1 and n2 are the number of moles of solvent and solute
respectively present in the solution. For dilute solutions n2 << where: R = gas constant (8.314 J/Kmol),
n1, hence neglecting n2 in the denominator we have Tf = freezing temperature in K,
M1 = Molar mass of solvent in Kg/mol,
p10  p1 n 2
 vapH = enthalpy of vapourisation of solvent in J/mol.
p10 n1

p10  p1 w 2  M1
or 
p10 M 2  w1

Here w1 and w2 are the masses and M1 and M2 are the molar
masses of the solvent and solute respectively.
5.2 Elevation in Boiling Point
Boiling point of a liquid is the temperature at which the vapour
pressure of the liquid becomes equal to the atmospheric pressure.
On addition of non-volatile solute the vapour pressure of the
The vapour pressure curve for solution lies below the curve
solvent decreases and therefore, to boil the solution the required
temperature will be higher. So, there will be a rise in the boiling for pure water. The diagram shows that Tb denotes the
point of the solution. elevation of boiling point of a solvent in solution

The increase in boiling point Tb = Tb – Tb0 where Tb0 is the

boiling point of pure solvent and Tb is the boiling point of
solution is known as elevation of boiling point.
Expression :
Tb  K b m

SCAN CODE
SOLUTIONS
SOLUTIONS 15
5.3 Depression in freezing point where : R = gas constant (8.314 J/K mol),
The freezing point of a substance may be defined as the Tf = freezing temperature in K,
temperature at which the vapour pressure of the substance in its M1 = Molar mass of solvent in Kg/mol,
liquid phase is equal to its vapour pressure in the solid phase.
fusH = enthalpy of fusion of solvent in J/kg
When a non-volatile solid is added to the solvent its vapour
pressure decreases and now it would become equal to that of
solid solvent at lower temperature. Thus, the freezing point of
the solvent decreases.

Tf  Tf0  Tf where Tf0 is the freezing point of pure solvent and
Tf is its freezing point when non-volatile solute is dissolved is
known as depression in freezing point.
Expression: Diagram showing Tf, depression of the freezing point
Tf  K f m of a solvent in a solution
5.4 Osmosis
Kf is known as Freezing Point Depression Constant or Molal
When a pure solvent and solution are kept with a semi-permeable
Depression Constant or Cryoscopic Constant.
membrane between them then the solvent particles pass through
Calculation of molar mass of solute : the membrane from the solvent side to the solution side. This
phenomenon is called “Osmosis”.
w2 / M2
m The semi-permeable membrane is a membrane that allows only
w1 /1000
small molecules to pass through and blocks the larger solute
Substituting this value of molality in equation we get : molecules.

Kf  w 2 / M2
Tf 
w1 /1000

K f  w 2  1000
Tf 
M 2  w1

K f  w 2  1000
M2 
Tf  w1

Kf :It is defined as the depression in freezing point when the

molality of the solution is unity. The unit of K f is
K kg mol-1.
Determination of Kf :

R  M1  Tf2
Kf 
1000   fus H

SCAN CODE
SOLUTIONS
SOLUTIONS 16
Osmotic pressure : pure solvent through the semi permeable membrane. This
The osmotic pressure of a solution is the excess pressure that phenomenon is called reverse osmosis.
must be applied to a solution to prevent osmosis, i.e., to stop the Application :
passage of solvent molecules through a semipermeable membrane Desalination of sea water :
into the solution.
When pressure more than osmotic pressure is applied, pure water
Patm   Patm is squeezed out of the sea water through the membrane.

6. ABNORMAL MOLAR MASSES

When the molecular mass of a substance determined by studying

any of the colligative properties comes out to be different than
the theoretically expected value, the substance is said to show
abnormal molar mass.
Abnormal Molar Masses are observed:
Solution Solvent 1. When the solute undergoes association in the solution.
The excess pressure equal to osmotic pressure must be 2. When the solute undergoes dissociation in the solution.
applied on the solution to prevent osmosis.
van’t Hoff Factor :
Expression :
To calculate extent of association or dissociation, van’t Hoff
For dilute solutions, osmotic pressure is proportional to the introduced a factor i, known as the van’t Hoff Factor.
molarity, C of the solution at a given temperature T. Thus:
Normal molar mass
  CRT i
Abnormal molar mass
Here  is the osmotic pressure and R is the gas constant.
Calculation of molar mass : Observed colligative property
i
Calculated colligative property
  (n 2 / V) RT

Here V is volume of a solution in litres containing n2 moles of Total no. of moles of particles after association (dissociation)

solute. If w2 grams of solute, of molar mass, M2 is present in the No. of moles of particles before association (dissociation)
solution, then n2 = w2 / M2 and we can write,
Association :
w 2 RT Number of particles will always decrease due to association
V 
M2 therefore i < 1.
nA  An
w RT
or M 2  2 Let initial particles (ni) = 1
V
Final number( nf) = 1 –  + /n
Isotonic solutions :
van’t Hoff factor, i = nf/ni = 1 –  + /n
Two solutions having same osmotic pressure at a given
temperature are called isotonic solutions. Dissociation :

The solution with lower concentration or lower osmotic pressure The number of particles will always increase due to dissociation
is known as “Hypotonic” with respect to more concentrated and hence i > 1.
solution. An  nA
The solution with higher concentration or higher osmotic pressure Initial particle = 1
is known as “Hypertonic” with respect to dilute solution. Final particles = 1 –  + n
Reverse osmosis : i = 1 –  + n
If a pressure larger than the osmotic pressure is applied to the
solution side, the solvent will flow from the solution into the

SCAN CODE
SOLUTIONS
SOLUTIONS 17

Modified Expressions :  Clausius-Clapeyron Equation

Relative lowering of vapour pressure of solvent,
p 2  H vap   1 1 
ln    
p10  p1 n p1  R   T1 T2 
 i. 2
p10 n1
where Hvap represents the enthalpy of vaporisation of the liquid.
Elevation of Boiling point Tb = i Kb m
8. OSTWALD WALKER METHOD
Depression of Freezing point, Tf = i Kf m
Osmotic pressure of solution,  = i n2 RT/V

7. VAPOUR PRESSURE

 Effect of temperature on vapour pressure

On increasing the temperature of the liquid the escaping tendency
of the molecules increases and the vapour pressure increases.
This is a typical method to measure the relative lowering in vapour
pressure of a solution. Dry air is passed successively through
three systems: solution, pure solvent and then a drying agent.
w1 and w2 represent the decrease in weight of the vessels and
w3 represents the increase in weight of the third vessel due to
absorption.
w1  PSOLUTION and w2  PSOLVENT – PSOLUTION
(as the air was already saturated)

Kinetic Energy  w3  PSOLVENT

The distribution of molecular kinetic Using the above relations the relative lowering in vapour pressure
can be calculated.
energies in a liquid

SCAN CODE
SOLUTIONS
SOLUTIONS 18

SUMMARY

 In case of dissociating solutes, i = 1 + (n – 1) 

 In case of associating solutes, i = 1 + (1/n – 1) 
 Corrected colligative properties:

p  ps in 2
   iCRT Tb  iK b m Tf  iK f m
ps n1

SCAN CODE
SOLUTIONS
SOLUTIONS 19

SOLVED EXAMPLES

Example - 1 (ii) mole fraction of sugar in the syrup.

Sol. (i) Weight of sugar syrup = 214.2 g
Why is an increase in temperature observed on mixing
chloroform with acetone ? Weight of sugar in syrup = 34.2 g

Sol. The bonds between chloroform molecules and molecules Weight of water in syrup = 214.2 – 34.2 = 180.0 g
of acetone are dipole-dipole interactions but on mixing, 34.2
the chloroform and acetone molecules start forming Moles of sugar =  0.1 (Molar mass = 342)
342
hydrogen bonds which are stronger bonds resulting in
the release of energy. This gives rise to an increase in 0.1
temperature. Molality = 1000 = 0.56 m.
180
Example - 2
34.2
(ii) Moles of sugar =  0.1
CCl4 and water are immiscible whereas ethanol and water 342
are miscible in all proportions. Correlate this behaviour
180
with molecular structure of these compounds. Moles of water =  10
18
Sol. CCl4 is non-polar covalent compound, whereas water is a
polar compound. CCl4 can neither form H-bonds with water 0.1
x  0.0099
molecules nor can it break H-bonds between water 10  0.1
molecules, therefore, it is insoluble in water.
Ethanol is a polar compound and can form H-bonds with Example - 5
water, which is a polar solvent, therefore it is miscible with
What is the mole fraction of the solute in 2.5 m aqueous
water in all proportions.
solution ?
Example - 3 Sol. 2.5 m aqueous solution means that 2.5 moles of solute are
present in 1000 g of water. Thus,
Differentiate between molality and molarity of solution.
What is the effect of change in temperature of a solution Moles of solute = 2.5
on its molality and molarity ? 1000
Moles of water =  55.6
Sol. Molarity is defined as number of moles of solute dissolved 18
in 1 L of the solution. Molality is defined as number of
moles of solute dissolved per kg of the solvent. Molarity 2.5
Mole fraction of solute = = 0.043.
is a function of temperature as volume depends on 2.5  55.6
temperature. With increase in temperature, volume of
solution increases, hence molarity decreases. Molality is Example - 6
not dependent on temperature because mass does not
A 6.90 M solution of KOH in water contains 30% by
change with temperature.
mass of KOH. Calculate the density of the KOH solution.
Example - 4 (Molar mass of KOH = 56 g mol–1).
Sol. 6.90 M solution of KOH contains 6.90 moles of KOH in
A sugar syrup of weight 214.2 g contains 34.2 g of sugar
1000 mL of solution.
(C12H22O11). Calculate :
Wt. of KOH in solution = 6.90 × 56 = 386.4 g
(i) molal concentration, and
Wt. of KOH in 1000 mL solution = 386.4 g
SOLUTIONS 20

Since the solution is 30% by weight, it means that 30 g of and Volume of solution = 200/1000 litre
KOH are present in 100 g of solution.
3.65  1000
 N  0 .5
100 36.5  200
 386.4 g of KOH is present in =  386.4
30
= 1288 g of solution N 0 .5
and M    0 .5
Valency 1
Weight 1288
Density   = 1.288 g mL–1
Volume 1000 1
(c) Eq. of H2SO4   2 ( Eq. = mole × valency)
10
Example - 7
Volume of solution = 500/1000 litre
Calculate the moles of methanol in 5 litres of its 2 m
solution, if the density of the solution is 0.981 kg L–1 2  1000 0.4
 N  0.4 and M  0.2
(Molar mass of methanol = 32.0 g mol–1). 10  500 2

Sol. Mass of 5L solution = 5L × 0.981 kg L–1 = 4.905 kg Example - 9

= 4905 g
Calculate the mole fraction of methanol in a solution
Mass of 2 m solution = 1000 g + 2 moles of methanol
containing 100 g of water and 50 g of methanol.
= 1000 + 2 × 32
Sol. Mole fraction of solute,
= 1000 + 64 = 1064 g
Now 1064 g of solution contains methanol = 2 mol Moles of solute
xB 
Moles of solute  Moles of solvent
4905 g of solution contains methanol
Mole fraction of methanol,
2
=  4905 = 9.22 mol.
1064 Moles of CH 3OH
x CH3OH 
Moles of CH 3OH  Moles of H 2 O
Example - 8

Calculate normality and molarity of the following : Mass of CH 3OH

Moles of CH3OH = Molar mass of CH OH
(a) 0.74g of Ca (OH)2 in 5 mL of solution. 3

(b) 3.65g of HCl in 200 mL of solution. Molar mass of CH3OH = 12 + 1 × 3 + 16 + 1 = 32 g mol–1

(c) 1/10 mole of H2SO4 in 500 mL of solution. 50
Moles of CH3OH   1.56 mol
32
0.74  w
Sol. (a)  Eq. of Ca(OH)2  Eq.   Now, moles of H2O
74 / 2  E
Volume of solution = 5 / 1000 litre Mass of H 2 O 100
= Molar mass of H O  18  5.56 mol
2
0.74  1000  2
N
74  5 So, the mole fraction of methanol,

1.56 1.56
N 4 x CH3OH   = 0.219
N=4  M   2 1.56  5.56 7.12
Valency 2

3.65
(b)  Eq. of HCl 
36.5
SOLUTIONS 21

Example - 10
Given mass  18 
  moles
A solution is 25% water, 25% ethanol and 50% acetic Molar mass  180 
acid by mass. Calculate the mole fraction of each
Also, the volume of solution = 500 cm3. Therefore,
component.
Sol. Let the total mass of solution = 100 g 18
Molarity   1000 = 0.2 M
Mass of water = 25 g 180  500
Mass of ethanol = 25 g Example - 12
Mass of acetic acid = 50 g
The solubility of Ba (OH)2.8H2O in water at 288 K is 5.6 g
25 per 100 g of water. What is the molality of hydroxide ion
Moles of water =  1.388
18 in saturated solution of Ba (OH)2.8H2O at 288 K.
( Molar mass of H2O = 18) Sol. The molar mass of Ba (OH)2.8H2O is

25 = 137 + 2 × 17 + 8 × 18
Moles of ethanol =  0.543
46 = 137 + 34 + 144 = 315

( Molar mass of C2H5OH = 46) Ba (OH)2  Ba2+ + 2OH–

Suppose x is molality of Ba2+ ions, molality of (OH)– is 2x.
50
Moles of acetic acid =  0.833 100 g water has 5.6 g of Ba (OH)2.8H2O
60
( Molar mass of CH3COOH = 60) 5.6
1000  56g
 1000 g water will have
100
Total number of moles = 1.388 + 0.543 + 0.833 = 2.764

1.388 56
Mole fraction of water = = 0.502 Moles of Ba (OH)2.8H2O =  0.178 mol
2.764 315
 Molality of hydroxyl ion = 0.178 × 2 = 0.356 m
0.543
Mole fraction of ethanol = = 0.196
2.764
Example - 13
0.833
Mole fraction of acetic acid = = 0.302
2.764 Calculate the normality of the resulting solution made
by adding 2 drops (0.1 mL) of 0.1N H2SO4 in 1 litre of
distilled water.
Example - 11
Sol.  Meq. of solute does not change on dilution
–1
Consider 18 g of glucose (molar mass 180 g mol ) to be Meq. of H2SO4 (conc.) = Meq. of H2SO4 (dil.)
present in 500 cm3 of its aqueous solution. What is the
0.1 × 0.1 = N × 1000 ( Meq. = N × V in mL)
molarity of the solution ?
N = 10–5N.
Number of moles of solute
Sol. Molarity   1000 Example - 14
Volume in mL
State Raoult’s law for solutions of volatile liquids. Taking
Here, solute is glucose whose mass = 18 g and molar mass suitable examples explain the meaning of positive and
= 180 g mol–1. Therefore, negative deviations from Raoult’s law.
Number of moles of glucose = Sol. Raoult’s law : It states that for a solution of volatile liquids
the partial pressure of each component is directly
proportional to its mole fraction.
SOLUTIONS 22
Mathematically,

pA  x A pB  x B p  p C7 H16  p C8H18 = 52.6 + 23.4 = 76.0 kPa

p A  p oA x A p B  p oB x B (iii) Mole fraction of octane (y C8H18 ) in the vapour phase.

Positive deviation from Raoults law : In this type of p C8H18  yC8H18 p total
deviation the partial pressure of each component of
solution is greater than that calculated from Raoults’s law, 23.4  yC8H18  76.0
i.e., p A  p oA x A & p B  p oB x B .
Example : A solution of water and ethanol.
23.4
yC8H18  = 0.308
76.0
Negative deviation from Raoult’s : In this type of deviation
the partial pressure of each component of solution is less Example - 16
than that expected from Raoult’s law, i.e., p A  p x A & o
A
At 300 K, the vapour pressure of an ideal solution containing
p B  p oB x B . one mole of A and 3 mole of B, is 550 mm of Hg. At the same
temperature, if one mole of B is added to this solution, the
Example : A solution of acetone and chloroform.
vapour pressure of solution increases by 10 mm of Hg.
Example - 15 Calculate the V.P. of A and B in their pure state.

Heptane and octane form an ideal solution at 373 K, The Sol. Initially, PM  PA0 . X A  PB0 . X B
vapour pressures of the pure liquids at this temperature
are 105.2 kPa and 46.8 kPa respectively. If the solution 1 3
550  PA0 .  PB0 .
contains 25g of heptane and 28.5g of octane, calculate 1 3 1 3
(i) vapour pressure exerted by heptane
or PA0  3PB0  2200 ..........(1)
(ii) vapour pressure exerted by solution
(iii) mole fraction of octane in the vapour phase. When, one mole of B is further added to it

Sol. p oC7 H16  105.2 kPa, p oC8H18  46.8 Kpa PM  PA0 . X A  PB0 . X B

M C7 H16  100g mol 1 , M C8 H18  114 g mol1 1 4

560  PA0 .  PB0 .
1 4 1 4
25
n C7H16   0.25  PA0  4PB0  2800 ......... (2)
100
Solving Eqs. (1) and (2), we get
28.5
n C8H18   0.25
114 PA0  400 mm, PB0  600 mm.

n C7 H16 Example - 17
0.25
x C7H16    0.5
n C7H16  n C8H18 0.25  0.25 Benzene and toluene form two ideal solutions A and B at
313K. Solution A contains 4 mole of the toluene and one
x C8H18  1  x C7H16  1  0.5  0.5 mole of C6H6. Solution B contains equal masses of toluene
and benzene. Calculate total pressure in each case. The
(i) p C7 H16  pC7H16 x C7H16 = 105.2 × 0.5 = 52.60 kPa
o
vapour pressure of C6H6 and toluene are 160 and 60 mm
respectively at 313 K.
(ii) p C8 H18  p C8H18 x C8H18  46.8  0.5
o

Sol. A : PM  PB  PT  PB0 . X B  PT0 . X T

p C8H18 = 23.4 kPa
1 4
 XB  and X T 
1 4 1 4
SOLUTIONS 23

Sol. On adding cyclohexane, its molecules get in between the

1 4
PM  160   60  ; molecules of ethanol thus breaking the hydrogen bonds
1 4 1 4
and reducing ethanol-ethanol interactions. This will
= 32 + 48 = 80 mm increase the vapour pressure of the solution and result in
positive deviation from Raoult’s law.
w / 78 w / 92
B: PM  160   60 
w w w w
 
78 92 78 92 Example - 20
(Given, equal weights are mixed) What is the effect of temperature on the solubility of a
solid solute in a liquid solvent ?
92 78
 160   60 
170 170 Sol. Solubility of solid in liquid is significantly affected by
temperature changes. This is because of dynamic
= 86.588 + 27.529 = 114.117 mm equilibrium which follow Le Chatelier’s principle. For
Example - 18 saturated solution such as NaNO3, KNO3, etc. the solubility
increases with increase of temperature because in these
At 298 K, the vapour pressure of pure ethyl alcohol is 44 substances, the process of dissolution is endothermic.
torr and that of pure benzene is 100 torr. Assuming ideal Solute + Solvent + Heat  Solution
behaviour, calculate the vapour pressure at 298 K of a
There are few substances such as cerium sulphate, lithium
solution which contains 10.0g of each substance (At.
carbonate, etc. whose solubility decreases with increase
wt., C = 12, H = 1, O = 16)
of temperature. This is because the process of dissolution
Sol. Wt. of benzene, C6H6 = 10.0g; molar mass of C6H6 is exothermic (sol. H < 0).
= (6 × 12) (6 × 1) = 78 g; wt. of ethyl alcohol, C2H5OH
Example - 21
= 10.0g; molar mass of C2H5OH = (2 × 12) + (5 × 1) + 16 + 1
= 46.0g. Define the following terms :-
10 (i) Dissolution (ii) Crystallisation
Thus : No. of moles of C6H6 = = 0.128;
78 (iii) Saturated solution
Sol. (i) When a solid solute is added to the solvent, some
10 solute dissolves and its concentration increases in
No. of moles of C2H5OH = = 0.217
46 solution. This process is known as dissolution.
(ii) Some solute particles in solution collide with the solid
0.128
X C6H 6   0.371; solute particles and get separated out of solution. This
0.128  0.217
process is known as crystallisation.
X C2 H5OH  1  0.371  0.629 (iii) A solution in which no more solute can be dissolved
at the same temperature and pressure is called a
PC 6 H 6  PC06 H 6 X C 6 H 6  (0.371) (100) = 37.1 torr.; saturated solution.

PC 2 H 5OH  PC0 2 H 5OH X C 2 H 5OH  (0.629) (44) = 28 torr.. Example - 22

Total pressure = 37.1 + 28 = 65.1 torr. What is the effect of pressure on the solubility of
(a) gases in liquids and (b) solids in liquids ?
Example - 19 Sol. (a) Solubility of gases in liquid increases with the increase
of pressure at a particular temperature. If the system
Why does a solution of ethanol and cyclohexane show
is in dynamic equilibrium, then the rate of dissolution
positive deviation from Raoult’s law ?
is equal to the rate of evaporation. If the pressure
increases over the system, the number of gaseous
particles per unit volume increases. As a result, more
SOLUTIONS 24

particles strike the surface of the solution and enter it. process difficult for the aquatic species.
Thus, a new equilibrium is established. Hence, on
increasing the pressure, the solubility of gases in liquid Example - 26
also increases.
Why oxygen mixed with helium is used by deep sea
(b) Pressure has very little effect on the solubility of a divers ?
solid in a liquid because solids have definite shape
Sol. Deep sea divers must cope with high concentration of
and volume; whereas liquids have definite volume but
dissolved gases while breathing air at high pressure under
not shape. Hence, solids and liquids cannot be
water as according to Henry’s law, solubility of gases
compressed much by increase in pressure.
increases with pressure. However, when the divers come
Example - 23 towards the surface, the pressure gradually decreases. This
releases the dissolved gases and leads to the formation of
Give an example of a solution containing a liquid solute bubbles of nitrogen in the blood. This blocks capillaries
in a solid solvent. and creates a medical condition known as bends. To avoid
Sol. An example of a solution containing a liquid solute in a bends and also the toxic effect of high concentration of
solid solvent is amalgam of mercury (Hg) with sodium (Na). nitrogen in the blood, the tanks used by divers are filled
In this solution, sodium is solid solvent and mercury is with air diluted with helium. Value of KH for He is 144.97
liquid solute. kbar and N2 is 76.08 kbar, therefore He has a lower solubility.
Example - 24 Example - 27

State Henry’s Law. What is the significance of KH ? What is meant by colligative properties ? Give
Sol. Henry’s law : It state that “the partial pressure of the gas expressions for any two.
in vapour phase (p) is proportional to the mole fraction of Sol. Colligative properties are the properties of solutions which
the gas (x) in the solution” and is expressed as depend only on the relative numbers of solute and solvent
p = KHx particles, but not on the nature of the solute. The four
important colligative properties are as follows :
where, KH is the Henry’s law constant.
(a) Relative lowering of vapor pressure.
Significance of K H. As p A = KHxA. Thus at constant
(b) Elevation in boiling point.
temperature for the same partial pressure of different gases,
x A  1/K H. In other words solubility is inversely (c) Depression in freezing point.
proportional to Henry’s constant of the gas. Higher the (d) Osmotic pressure.
value of KH, lower is the solubility of the gas. As H2 is Relative lowering of vapor pressure : In the presence of a
more soluble than helium, H2 will have lower value KH non-volatile solute, the vapor pressure of the solution
than that of helium. becomes lower than the vapor pressure of pure solvent.
The relative lowering of vapor pressure is
Example - 25
p  (p oA  p A ) / p oA
Why are the aquatic species more comfortable in cold
water rather than warm water ? where p oA is the vapor pressure of pure solvent. The relative
Sol. The aquatic species are more comfortable in cold water lowering depends only on the concentration of the solute
rather than warm water because the solubility of gas in and not in nature of solute
liquid decreases with increase in temperature, and increases
p  p oA x B
with decrease in temperature. Therefore, the percentage of
oxygen present in cold water will be more because in cold where xB is the mole fraction of the solute.
water, solubility of oxygen gas in water will be more than in
Osmotic pressure : When two solutions of different
hot water. Now, we know that oxygen is essential for
concentration are separated by a semiperimeable membrane,
respiration or breathing. Hence, the aquatic species are
the solvent shows a tendency to move from dilute to
comfortable in cold water; whereas in hot water, the
concentrated solution. This property is known as osmosis.
concentration of oxygen is less which makes the breathing
SOLUTIONS 25

This uneven passage of the solvent creates pressure called Example - 30

osmotic pressure. It can be measured by determining the
amount of counter pressure needed to prevent osmosis. It A solution is made by dissolving 30 g of a non-volatile
is proportional to concentration and temperature of the solute in 90 g of water. It has a vapour pressure of
solution and is given by 2.8 kPa at 298 K. At 298 K, the vapour pressure of pure
water is 3.64 kPa. Calculate the molar mass of solute.
  CRT
Sol. Let the molar mass of non-volatile solute be MB
Expressing concentration in terms of moles per liter, we
have 90 30
Moles of water   5, Moles of solute =
MB
nB 18
 RT
V Applying Raoult’s law,
where nB is the number of moles of the solute.
p 0  ps w B M A
 
Example - 28 p0 MB wA

Why does vapour pressure of a liquid decrease when a 3.64  2.8 30 18

non-volatile solute is added into it ?  
3.64 M B 90
Sol. It is because some liquid molecules at the surface are
replaced by the molecules of the solute which are non- 0.84 6
volatile. 
3.64 M B
Example - 29
6  3.64
MB 
Derive an equation to express that relative lowering of 0.84
vapour pressure for a solution is equal to the mole fraction
MB = 26 g mol–1
of the solute in it when the solvent alone is volatile.
Sol. For a solution of volatile liquids Raoult’s law, is given as Example - 31
p = pA + p B The vapour pressure of pure benzene at a certain
If solute (component B) is nonvolatile then temperature is 0.850 bar. A non-volatile, non-electrolyte
solid weighing 0.5 g when added to 39.0 g of benzene
p  p A  p oA x A
(molar mass 78 g mol–1), then vapour pressure of the
p  p oA (1  x B ) solution is 0.845 bar. What is the molar mass of the solid
substance ?
p  p oA  p oA x B Sol. The various quantities known to us are as follows :

p oA x B  p oA  p PAo  0.850 bar; p = 0.845 bar; MA = 78 g mol–1;

wB = 0.5 g; wA = 39 g
p oA  p
 xB Substituting these values in equation
p oA

Thus, relative lowering of vapour pressure is equal to the p oA  p w B  M A

 , we have
mole fraction of non-volatile solute. p1o MB  w A

0.850 bar  0.845 bar 0.5 g  78 g mol1


0.850 bar M B  39 g

Thus, MB = 170 g mol–1.

SOLUTIONS 26

Example - 32 Example - 34

What weight of the non-volatile urea (NH2 – CO – NH2) The boiling point of chloroform was raised by 0.325ºC
needs to be dissolved in 100 g of water in order to decrease when 0.5141 g of anthracene was dissolved in 35g
the vapour pressure of water by 25% ? What will be of chloroform. Calculate the molecular weight of
molality of the solution ? anthracene. (K b = 39.0 per 100 g of chloroform)

p o  p s 25 Sol. wt. of solute, W2 = 0.5141g ; wt. of solvent,

po  ps 25
Sol. Here,  or 
po 100 ps 75
35
W1 = kg = 0.035 kg;
wA = 100 g, WB = ? 1000

For urea, MB = 60 g mol–1 Tb = 0.325ºC ; Kb = 39ºC (100 g mol–1)

For water, MA = 18 g mol–1
100
= 39ºC × kg mol1
1000
p o  ps n B w B / M B
 
ps nA w A / MA = 3.9ºC kg mol–1 ; mol. wt. of anthracene, M2 = ?

25 w B / 60 K b  W2 in g
  We know that Tb  ;
75 100 /18 M 2  W1 in kg

or wB = 111 g
K b  W2 in g
M2 
111g 1 Tb  W1 in kg
Molality of the solution = 1
  1000g kg 1
60 g mol 100 g
3.9º C kg mol 1  0.5141g
= 18.5 mol kg–1 or 18.5 m Or M 2   176.26g mol 1
0.325º C  0.035 kg
Example - 33
Example - 35
A solution prepared by dissolving 1.25 g of oil of winter
green (methyl salicylate) in 99.0 g of benzene has a boiling Calculate the molal elevation constant of water, it being
point of 80.31ºC. Determine the molar mass of this given that 0.1 molal aqueous solution of a substance
compound. (Boiling point of pure benzene boiling at 100.052 ºC.
= 80.10 ºC and Kb for benzne = 2.53 ºC molal–1.) Sol. Molality of solution, m = 0.1 molal; the boiling point of
Sol. The molar mass MB of solute can be calculated from the solution Tb = 100.052 ºC. Therefore, Tb  Tb  Tbo is the
relation,
elevation in the boiling point, Tb  100.052 – 100 = 0.052
K b  w B  1000 ºC. By applying the relationship, Tb  K b m we get
MB 
Tb  w A
Tb 0.052 º C
Mass of solute, wB = 1.25 g, mass of solvent, wA = 99 g, Kb   –1
m 0.1 molal = 0.52 ºC molal
elevation in boiling point, (Tb) = 80.31 – 80.10 = 0.21 ºC.
Kb for benzene = 2.53 ºC molal–1. Molal elevation constant Kb = 0.52 ºC molal–1.

2.53 1.25 1000

MB  = 152.11 g mol–1
0.21 99
SOLUTIONS 27
Example - 36 Example - 38

Define molal boiling point elevation constant and molal Ethylene glycol (molar mass = 62 g mol–1) is a common
freezing point depression constant. Explain the cause automobile antifreeze. Calculate the freezing point of a
for elevation in boiling point and depression in freezing solution containing 12.4 g of this substance in 100 g of
point when non-volatile solute is added to a solvent. water. Would it be advisable to keep this substance in
Sol. Molal boiling point elevation constant : It may be defined the car radiator during summer ?
as the elevation in boiling point when the molality of Given : Kf for water = 1.86K kg/mol
solution is unity i.e., 1 mol of solute is dissolved in
Kb for water = 0.512K kg/mol
1 kg (1000 g) of the solvent. The units of molal elevation
constant is degree molality–1 i.e., K molal–1 or ºC molal–1 or K w B 1000
Sol. Tf  K f  
kg mol–1. It is denoted by Kb. mB w A
Molal freezing point elevation constant : It may be defined
as the depression in freezing point when the molality of 12.4 1000
 1.86    3.72 K
the solutions is unity i.e., 1 mol of the solute is dissolved 62 100
in 1000 g (1 kg) of the solvent. It is denoted by Kf. The unit
since water freezes at 0ºC, so freezing point of the solution
of Kf is degree molality–1 i.e., K molal–1 or K kg mol–1. containing ethylene glycol will be – 3.72
Cause of elevation in boiling point : Vapor pressure of the
solution is lower than that of pure solvent. Hence, when w B 1000
Tb  K b  
the non-volatile solute is added to pure solvent, the MB w A
solution has to be heated more to make vapor pressure
equal to the atmospheric pressure. 12.4 1000
 0.512    1.024 K
Cause of depression in freezing point : Vapor pressure of
62 100
the solution is less than that of pure solvent. Freezing
Tb  Tbo  Tb  100  1.024 = 101.024 ºC
point of a substance is the temperature at which the solid
and the liquid forms of the substance are in equilibrium since water boils at 100ºC, so a solution containing ethylene
i.e., the solid and the liquid forms of substance have the glycol will boil at 101.024ºC, so it is advisable to keep this
same vapor pressure. Therefore, for the solution, this will substance in car radiator during summer.
occur at a lower temperature.
Example - 39
Example - 37
Ethylene glycol (C2H6O2) is used as an antifreeze. What
Explain why the freezing point of a solution is lower than mass of ethylene glycol should be added to 5.00 kg of
the freezing point of the pure solvent. water to lower the freezing point to –5.0 ºC ? Given that
Sol. Freezing point of a substance may be defined as the Kf = 1.86 ºC molal–1. Consider ethylene glycol to be a
temperature at which the vapor pressure of the substance non-electrolyte.
in its liquid phase is equal to its vapor pressure in the solid Sol. Given that Tf = 5.0 ºC and Kf = 1.86 ºC molal–1.
phase. The freezing point of a solution is lower than that
Therefore, molality is
of the pure solvent because the vapor pressure of solution
is less than that of pure solvent. So according to Raoult’s T 5.0
law, when a non-volatile solid is added to the solvent, its Molality    2.7 molal
K f 1.86
vapor pressure decreases and it becomes equal to that of
solid solvent at a lower temperature. The decrease in the Therefore, the number of moles of ethylene glycol is found
freezing point is known as depression of freezing point, from the relation
and it is denoted by Tf.
Number of moles of solute
Molality 
Mass of solvent
SOLUTIONS 28

n where Kf is the molal depression constant, wB is the given

 2.7  n  13.5 mol mass of solute, MB is the molar mass of solute, wA is the
5.00
given mass of solvent (water). Substituting given values,
Molar mass of ethylene glycol is = 2 × 12 + 4 × 1 + 2 × 16 = we get
62 g mol–1. Hence, the mass of ethylene glycol to be added
to water is 1.86  54 1000 100440
Tf    2.23K
180  250 45000
62 g
13.5 mol  = 837 g Therefore, the freezing point of the solution
mol
= 0 – 2.23 = – 2.23 K.
Example - 40
Example - 42
A 0.1539 molal aqeuous solution of cane sugar (molar
mass = 342 g mol–1) has a freezing point of 271 K, A sample of naphthalene has freezing point, 80.6ºC.
whereas the freezing point of pure water is 273.15 K. When 0.512g of a solute is dissolved in 7.03g of
What will be the freezing point of an aqueous solution naphthalene, the solution has a freezing point of
75.2ºC. Calculate the molecular mass of the solute.
containing 5 g of glucose (molar mass = 180 g mol–1)
per 100 g of solution ? (K f for naphthalene = 6.8ºC kg/mol)

Sol. Molality of cane sugar solution = 0.1539 molal and the Sol. Tf = (80.6 – 75.2)ºC = 5.4ºC ;
depression of freezing point, Tf = 273.15 – 271 = 2.15 K. wt. of solute, W2 = 0.512 g;
from Tf = Kfm, we have
wt. of solvent, W1 = 7.03 g ;
Tf 2.15K mol. wt. of solute, M2 = ?, Kf = 6.8ºC kg mol–1.
Kf   o –1
m 0.1539 mol kg -1 = 13.97 C molal
We know that:
Amount of glucose in 100 g of solution = 5 g and amount
of water in 100 g of solution = 100 g – 5 g = 0.095 kg. K f (in º C kg mol 1 )  W2 (in g )
Tf  ;
Number of moles of glucose = 5/180 mol = 0.0278 mol and 1  W1 in g 
M 2 (in g mol )    kg
the molality of solution m = 0.0278 mol/0.095 kg = 0.2926  1000 
mol kg–1. So,
Tf = Kf × m = 13.97K kg mol–1 × (0.2926) = 4.08 K 6.8º C kg mol 1  0.512g
5.4º C 
Therefore, freezing point of glucose solution 7.03
M2  Kg
= 273.15 – 4.08 = 269.07K. 1000

Example - 41
6.8º C kg mol 1  0.512g
 M2   91.7 g mol 1
Calculate the temperature at which a solution containing 5.4º C  00703 kg
54 g glucose, (C6H12O6) in 250 g of water will freeze. (Kf
Example - 43
for water = 1.86 K molal–1)
Sol. Molar mass of glucose MB = 12 × 6 + 12 × 1 + 6 × 16 = 180 The freezing point of a solution of 4.0g CdI2 in 95g of
g mol–1. According to depression in freezing point, water was – 0.25ºC. Calculate the degree of dissociation
of salt. (K f for water = 1.85ºC kg/mol (At. wt. Cd =
K f  w B  1000
Tf  112; I = 127).
MB  w A
Sol. Wt. of solute, W2 = 4.0g ; wt. of solvent,
W1 = 0.095 kg;

K f  W2 in g
Tf = 0.25 ºC; M 2 
Tf  W1 in g
SOLUTIONS 29
values in Eq. (1), we get
1.85º C kg mol 1  4g
M
 2   311.6 mol 1
0.25º C  0.095 kg 0.1 0.0821 298
MB  = 13980 g mol–1
0.0175  0.01
Theoretical molar mass (MTh) of CdI2
Example - 46
= 112 + (2 × 127) = 366 g mol–1
For CdI2    Cd2+ + 2I– How is it that measurement of osmotic pressures is more
widely used for determining molar masses of
Initial conc. 1 0 0 macromolecules than the rise in boiling point or fall in
At equilibrium 1 – 2 freezing point of their solutions ?
i = 1 – + 2 = 1 + 2 ...... (1) Sol. The osmotic pressure method has the advantage over rise
in boiling point or fall in freezing point for determining
M Th 366g mol 1 molar masses of macromolecules because
But i = M  .......(2)
obs 311.6g mol 1 (i) Pressure measurement around the temperature and the
molarity of solution is used instead of molality.
Substituting the value of i from (2) in (1), we get
(ii) Compared to other colligative properties, its magnitude is
366 1  366  large even for very dilute solutions.
 1  2 or    1
311.6 2  311.6  Example - 47
or = 0.087 or 0.087 × 100 = 8.7 % dissociated
The vapour pressure of water at 293 K is 2338 Pa and the
Example -44 vapour pressure of an aqueous solution is 2295.8 Pa. If
density of solution is 1010 Kg/m3 at 313 K, calculate the
Define osmotic pressure and explain its origin. What is osmotic pressure at 313 K. Molecular weight of solute =
the effect of temperature on osmotic pressure ? 60.
Sol. Osmosis is the phenomenon of the flow of solvent through
a semipermeable membrane from pure solvent to the P 0  Ps n n  18
Sol. At 293 K ;  
solution. Osmotic pressure is the pressure applied on the Ps N W
solution side to just stop the flow of the solvent from its
side to the solution side across a semipermeable membrane. 2338  2295.8 n  18
The increase in temperature will increase the osmotic  
2295.8 W
pressure as   T.
n 42.2 1
Example - 45  W  2295.8  18
Consider 100 mg of a protein to be dissolved in just or W = 979.25 × ng
enough water to make 10.0 mL of solution. If this
solution has an osmotic pressure of 13.3 mm Hg at  Weight of solution = 979.25n + wt. of solute
25 ºC, what is the molar mass of the protein ? (Given = 979.25n + 60n = 1039.25 ng = 1.0393n kg
that R = 0.0821 L atm mol–1 K–1 and 760 mm
Weight 1.0393n
Hg = 1 atm).  Volume of solution   m3
( at 313 K ) density 1010
Sol. We know that osmotic pressure (  ) is given by
Now, PV = nRT
nRT w BRT
 and M B  (1)
V V 1.0393n
P  n  8.314  313
1010
where MB is the molar mass of protein;  = 13.3 mm
Hg = 13.3/760 = 0.0175 atm; V = 10 mL = 10/1000 = 0.01 L; R P = 2.53 × 106 Pa
= 0.0821 L atm mol–1K–1; T = 25 ºC = (273 + 25) K = 298 K;
wB = 100 mg = 100/1000 g = 0.1 g. Substituting all the
SOLUTIONS 30

Example - 48 Sol. In case of NaCl, the observed values of colligative

properties are greater than the calculated values because
The osmotic pressure of a non-volatile solute in C6H6 at in a dilute solution NaCl is expected to dissociate
25ºC is 20.66 Nm–2. If the solution had a concentration of completely. Therefore, NaCl has observed values twice the
2g/dm3, what is mol. wt. of solute ? calculated values of colligative properties.

Sol. Given that, NaCl  Na + +Cl –

 = 20.66 Nm–2, Example - 52

w 2 10 3 A 0.118 molal solution of LiCl has a freezing point of

 2g / dm 3  3
kg / m 3 –0.415 ºC. What is the van’t Hoff factor for this solute at
V 10
this concentration ?
R = 8.314 JK–1 mol–1, T = 273 + 25 = 298 K Sol. Molality of solution m = 0.118 molal. For LiCl, Kf = 1.86ºC
w molal–1 and Tf (measured) = 0.415ºC. Now, the depression
V  w RT
RT  m  in freezing point is found as
m V 
Tf (not ionized) = Kf × m
3
2 10  8.314  298 = (1.86 ºC molal–1) × 0.118 molal = 0.219 ºC
m 3 = 239.84 kg mol–1
10  20.66 The van’t Hoff factor can be calculated using relation
Example - 49 Tf (measured) 0.415 º C
i  = 1.89
Tf (not ionized) 0.219 º C
State the condition resulting in reverse osmosis.
Sol. Reverse osmosis will occur if a pressure higher than the Example - 53
osmotic pressure is applied on the solution.
What mass of NaCl (molar mass = 58.5 g mol–1) must be
Example - 50
dissolved in 65 g of water to lower the freezing point by
What is van’t Hoff factor and how is it related to the 7.5 ºC ? The freezing point depression constant Kf for
molar mass of the solute. water is 1.86 ºC molal–1. Assume van’t Hoff factor for
Sol. van’t Hoff factor is defined as the ratio of the observed NaCl to be 1.87.
value of colligative property to the calculated value of Sol. Given that molar mass, M = 58.5 g mol–1; van’t Hoff factor
colligative property. It is denoted by i. for NaCl, i = 1.87; freezing point depression constant, Kf
for water = 1.86 ºC molal–1 and Tf = 0 – (–7.5) = 7.5 ºC.
Observed value of the colligative property
i Now, applying the relation and substituting values, we get
Calculated value of the colligative property
T = i × Kf × m 7.5 = 1.87 × 1.86 × m m = 2.15 molal
van’t Hoff factor is inversely proportional to the molecular Grams of NaCl = 2.15 × 58.5 = 125.775 g per kg.
mass of the solute. Therefore,
If 125.775 g of NaCl is added to 1000 g of water, then for 1g
Normal molecular mass M 125.775
i  Calculated of water, the amount of NaCl to be added is and
Abnormal molecular mass M Observed 1000

Example - 51 (125.775  65)

for 65g of water, it is  8.175g
1000
Explain why in case of sodium chloride, the observed
Hence, mass of NaCl to be added = 8.175 g in 65 g of water.
values of colligative properties are greater than the
calculated values.
SOLUTIONS 31

Example - 54 of particles in 0.1 M NaCl solution is nearly double than

that in 0.1 M glucose solution. Freezing point depression,
(a) Urea forms an ideal solution in water. Determine the being a colligative property, is therefore, nearly twice for
vapour pressure of an aqueous solution containing NaCl solution than for glucose solution of same molarity.
10% by mass of urea at 40ºC.
Example - 55
(Vapour pressure of water at 40ºC = 55.3 mm
of Hg) (i) Benzoic acid completely dimerises in benzene. What
(b) Why is freezing point depression of 0.1 M sodium will be the vapour pressure of a solution containing
chloride solution nearly twice that of 0.1 M glucose 61g of benzoic acid per 500g benzene when the
solution ? vapour pressure of pure benzene at the temperature
of experiment is 66.6 torr ?
po  p
Sol. (a)  x urea (ii) What would have been the vapour pressure in the
po absence of dimerisation ?
Let the mass of solution be 100 g (iii) Derive a relationship between mole fraction and
 Mass of Urea = 10 g vapour pressure of a component of an ideal solution
in the liquid phase and vapour phase.
10 1
n urea   p
60 6 Sol. (i)  iX B
po
90
n H2 O  1
18 i
2
n H2 O  5
61
n urea 1/ 6 1/ 6 nB 122
x urea    XB  
n urea  n H 2O 1/ 6  5 31/ 6 nA  nB 61 500

122 78
1
x urea 
31 0.5 0.5
 
0.5  6.41 6.91
55.3  p 1

55.3 31 p 1 50
 
66.6 2 691
55.3
55.3  p 
31 50  66.6
p   2.41
691 2
55.3
 55.3  p po – p = 2.41
31
p = 66.6 – 2.40
 1 = 64.20 torr
 55.3 1    p
 31  (ii) In the absence of dimerisation.
i=1
30
p  55.3 
31 p
 XB
p = 53.52 mm Hg. po
(b) NaCl being an electrolyte, dissociates almost completely
50
to give Na+ and Cl– ions in solution whereas glucose being p   66.6  4.82
691
non-electrolyte, does not dissociate. Therefore, the number
SOLUTIONS 32
P = 66.6 – 4.82 = 61.78 torr

(iii) From Raoult’s law, p A  x A p oA and 1000  K f  w 2 1000  1.86 º C molal 1  0.5g
M2  
Tf  w 1 0.24 º C  100g
p B  x B p oB

where, xA = mole fraction of liquid A 930

  38.75g mol1
24
p A  x A p oA
Molar mass of KCl = 39 + 35.5 = 74.5 g mol–1.
xB = mole fraction of liquid B p B  x B p o
B Therefore, van’t Hoff factor is
yA = Mole fraction of component – 1 in vapour phase.
yB = Mole fraction of component – 2 in vapour phase. Calculate molecular mass 74.5
i   1.92
Observed molecular mass 38.75
pA pA
yA  
p total p A  p B Now, KCl dissociates as
KCl  K+ + Cl–
p pB
yB  B  Initial moles 1 mol 0 0
p total p A  pB
Moles after dissolution 1– 
xAp o
xAp o
Total number of moles after dissociation = 1 –  +  +  =
yA  A
 A
x A p A  x B p B x A p A  (1  x A ) p oB
o o o
1 + . Therefore,

1 
x B p oB i    i  1  1.92  1  0.92
yB  1
x A poA  x B p oB
Therefore, percentage ionization = 0.92 × 100 = 92%.
Example - 56 Example - 58
In an aqueous solution, KCl undergoes complete Phenol associates in benzene to a certain extent to form
dissociation into K+ and Cl– ions. What is the value of dimers. A solution containing 2.0 × 10–2 kg of phenol in
osmotic pressure of a 0.525M solution of KCl at 300 K ? 1.0 kg of benzene has its freezing point decreased by
(Use R = 0.0821 L atm K–1) 0.69 K. Calculate the degree of association of phenol (Kf
Sol. As KCl dissociates K+ and Cl– ions, for benzene = 5.12 K molal–1)
i=2 Sol. Mass of phenol, w2 = 2.0 × 10–2 kg; Kf = 5.12 K molal–1;
mass of benzene, w1 = 1.0 kg; Tf = 0.69 K. Therefore,
Osmotic pressure ( ) can be determined using the formula
according to the equation
 = iCRT = 2 × 0.525 × 0.0821 × 300 = 25.86 atm
1000 K f w 2
Example - 57 M2 (observed) = w1Tf

When 0.5 g KCl was dissolved in 100 g water, the solution

originally at 20 ºC, froze at – 0.24 ºC. Calculate the 1000g  5.12K kg mol 1  2.0  102 kg 10.240  10 2
 
percentage ionization of salt. Kf per 1000 g of water = 1.0 kg  0.69 K 0.69
1.86 ºC molal–1. = 14840.58 × 10–2 = 148.4 g mol–1
Sol. Mass of solute KCl, w2 = 0.5 g; mass of solute H2O, w1 = Also, M2 (calculated) for C6H5OH
100g. Molar mass of H2O, M1 = 1 × 2 + 16 = 18 g mol–1 and
= 12 × 6 + 1 × 5 + 16 + 1 = 94 g mol–1. Therefore,
Tf = 0 – (–0.24) = 0.24 ºC. According to the equation,
SOLUTIONS 33

M 2 (calculated) 4 Example - 60
i   0.633
M 2 (observed) 148.4
A 5% solution (by mass) of cane -sugar in water has freezing
2C6H5OH  (C6H5OH)2
point of 271 K. Calculate the freezing point of 5% solution
Initial moles 1 mol
(by mass) of glucose in water if the freezing point of pure
Moles after dissociation 1–  /2
water is 273.15 K.
 
Total moles after dissociation = 1     1  . Therefore, [Molecular masses : Glucose C6H12O6 : 342 amu]
2 2
Sol. Molality of sugar solution
1  ( / 2)
i
1 w 2  1000 5 1000
    0.154 m
or  = 2 (1 – i) = 2 (1 – 0.633) = 0.734 M 2  W1 342 95
Tf  Tfo  Tf  273.15  271  2.15 K
Example - 59
Tf 2.15
Tf  K f m K f  
Nalorphene (C19H21NO3), similar to morphine, is used to m 0.154

combat withdrawal symptoms in narcotic users. Dose of

Molality of glucose solution
nalorphene generally given is 1.5 mg. Calculate the mass of
1.5 × 10-3m aqueous solution required for the above dose. w 2  1000 5 1000
    0.292 m
M 2  W1 180 95
Sol. The molar mass of Nalorphene (C19H21NO3) is given as:

19 × 12 +12 × 1 + 1 × 14 + 3 × 16 = 311 g mol-1 2.15

 f(Glucose) = Kf × m =  0.292  4.08
0.154
In 1.5 × 10-3 m aqueous solution of nalorphene, 1 kg

(1000 g) of water contains 1.5 × 10-3 mol  Freezing point of glucose solution

= 1.5 × 10-3 × 311 g = 0.4665 g = 273.15 – 4.08 = 269.07K

Therefore, total mass of the solution

= (1000 + 0.4665) g = 1000.4665 g

This implies that the mass of the solution containing 0.4665

g of nalorphene is 1000.4665 g.

Therefore, mass of the solution containing 1.5 mg of

nalorphene is:

1000.4665  1.5  103

g  3.22g
0.4665

Hence, the mass of aqueous solution required is 3.22 g.

SOLUTIONS 34

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Concentration Terms (c) 1.8 M (d) 0.18 M
–1
1. What is the mass percentage of carbon tetrachloride if 22g 10. 150 mL of C2H5OH (density = 0.78g ml ) is diluted to one
of benzene is dissolved in 122g of carbon tetrachloride ? litre by adding water. Molarity of the solution is
(a) 84.72% (b) 15.28 % (a) 2.54 Mol/litre (b) 11.7 Mol/litre
(c) 50% (d) 44% (c) 2.99 Mol/litre (d) 29.9 Mol/litre
2. A solution is obtained by mixing 200 g of 30% and 300 g of 11. How many grams of a dibasic acid (Mol. wt. = 200) should
20% solution by weight. What is the percentage of solute be present in 100 mL of its aqueous solution to give
in the final solution ? decinormal strength ?
(a) 50% (b) 28% (a) 1g (b) 2g
(c) 64% (d) 24% (c) 10g (d) 20g.
3. What is the mole fraction of glucose in 10% w/w glucose 3
12. The normality of 10% H2SO4 solution (d = 1.1g/cm ) is
solution ?
(a) 2.04 (b) 1.02
(a) 0.01 (b) 0.02
(c) 1.85 (d) 2.25
(c) 0.03 (d) 0.04
13. An aqueous solution of urea containing 18g urea in
4. Rectified spirit contains 95% ethanol by weight. The mole 3
1500 cm of the solution has a density equal to
fraction of ethanol will be 3
1.052 g/cm . If the molecular weight of urea is 60, then the
(a) 0.881 (b) 0.99
molality of the solution is
(c) 0.118 (d) 0.81
(a) 0.200 (b) 0.192
5. The mole fraction of C2H5OH (Mol. wt. = 46) in 5 molal
(c) 0.100 (d) 1.200
aqueous ethyl alcohol solution is
(a) 0.082 (b) 0.82
Raoult's Law
14. The vapour pressure of a pure liquid A is 70 torr at 27ºC. It
5 forms an ideal solution with another liquid B. The mole
(c) 5 (d)
55.55 fraction of B is 0.2 and total vapour pressure of the solution
is 84 torr at 27ºC. The vapour pressure of pure liquid B at
6. What will be the molality of a solution of glucose in water
27ºC. (torr)
which is 10 % w/w ?
(a) 14 (b) 56
(a) 0.01 m (b) 0.617 m
(c) 140 (d) 70.
(c) 0.668 m (d) 1.623 m
15. The vapour pressure of water at room temperature is 23.8
7. What is the molarity of a solution containing 10g of NaOH
mm Hg. The vapour pressure of an aqueous solution of
in 500 mL of solution ?
sucrose with mole fraction 0.1 is equal to
(a) 0.25 mol L–1 (b) 0.75 mol L–1
(a) 23.9 mm Hg (b) 24.2 Hg
(c) 0.5 mol L–1 (d) 1.25 mol L–1 (c) 21.42 mm Hg (d) 21.44 mm Hg.
8. What will be the molarity of 30 mL of 0.5 M H2SO4 solution 16. Liquid A and B form an ideal solution. If vapour pressure
–2 –2
when diluted to 500 mL ? of pure A and B are 500 Nm and 200 Nm respectively,
(a) 0.3 M (b) 0.03 M the vapour pressure of a solution of A in B containing 0.2
(c) 3 M (d) 0.103 M mole fraction would be
–2 –2
9. To a 4 L of 0.2 M solution of NaOH, 2 L of 0.5 M NaOH is (a) 700 N m (b) 300 N m
added. The molarity of resulting solution is : –2 –2
(c) 260 N m (d) 140 N m
(a) 0.9 M (b) 0.3 M
SOLUTIONS 35

17. 3 moles of P and 2 moles of Q are mixed, what will be their (a) A – B interactions are stronger than A – A and B – B
total vapour pressure in the solution if their pure component interactions
vapour pressures are 80 and 60 torr respectively ? (b) A – B interactions are weaker than A – A and B – B
(a) 80 torr (b) 140 torr interactions

(c) 72 torr (d) 70 torr (c) vapour pressure of solution is more than the pure
components
18. Intermolecular forces between n-hexane and n-heptane are
nearly same as between hexane and heptane individually. (d) vapour pressure of solution is less since only one
When these two are mixed, which of the following is not component vaporises.
true about the solution formed ? 22. When acetone and chloroform are mixed together, hydrogen
bonds are formed between them. Which of the following
(a) It obeys Raoult’s law, i.e. pA = x A p oA and p B  x B p oB
statements is correct about the solution made by mixing
(b) H mixing is zero. acetone and chloroform ?
(a) mixing acetone and chloroform will form an ideal solution
(c) Vmixing is zero. (b) On mixing acetone and chloroform, positive deviation
is shown since the vapour pressure increases.
(d) It forms minimum boiling azeotrope.
(c) On mixing acetone and chloroform, negative deviation
19. The vapour pressure of pure benzene and toluene are 160
is shown since there is decrease in vapour pressure.
and 60 torr respectively. The mole fraction of toluene in
(d) At a specific composition acetone and chloroform will
vapour phase in contact with equimolar solution of benzene
form minimum boiling azeotrope.
and toluene is
(a) 0.50 (b) 0.6 Concept of Boiling & Azeotropes
(c) 0.27 (d) 0.73 23. Given below are few mixtures formed by mixing two
components. Which of the following binary mixtures will
20. Study the figures given below and mark the correct
have same composition in liquid and vapour phase at a
statement.
particular value of P, T ?
(i) Ethanol + Chloroform (ii) Nitric acid + Water
(iii) Benzene + Toluene
(iv) Ethyl chloride + Ethyl bromide
(a) (i) and (iii) (b) (i) and (ii)
(c) (i), (ii) and (iii) (d) (iii) and (iv)
Colligative Properties Of Dilute Solutions
(a) (i) Nitric acid + Water, (ii) Acetone + Ethyl alcohol 24. 2g of sugar is added to one litre of water to give sugar
(b) (i) Water + Ethyl alcohol, (ii) Acetone + Benzene solution. What is the effect of addition of sugar on the
boiling point and freezing point of water ?
(c) (i) Acetone + Ethyl alcohol (ii) Acetone + Chloroform
(a) Both boiling point and freezing point increase.
(d) (i) Benzene + Chloroform (ii) Acetone + Chloroform
(b) Both boiling point and freezing point decrease.
21. Two liquids HNO3 (A) and water (B) form a maximum boiling
(c) Boiling point increases and freezing point decreases.
azeotrope when mixed in the ratio of 68% and 32%
respectively. It means
SOLUTIONS 36
(d) Boiling point decreases and freezing point increases. (a) 53.06g mol–1 (b) 25.3 g mol–1
25. In three beakers labelled as (A), (B) and (C), 100 mL of (c) 16.08g mol–1 (d) 43.92g mol–1
water, 100 mL of 1M solution of glucose in water and
100 mL of 0.5 M solution of glucose in water are taken 31. If 1g of solute (molar mass = 50g mol–1) is dissolved in 50g
respectively and kept at same temperature. of solvent and the elevation in boiling point is 1K. The
molar boiling constant of the solvent is
(a) 2 (b) 3
(c) 2.5 (d) 5
32. The molal elevation constant for water is 0.56ºC per kg of
water. The boiling point of solution made by dissolving
Which of the following statements is correct ?
6.0g of water (NH2CONH2) in 200g of water is
(a) Vapour pressure in all the three beakers is same.
(a) 10.028ºC (b) 100.28ºC
(b) Vapour pressure of beaker B is highest.
(c) 50.14ºC (d) none of these
(c) Vapour pressure of beaker C is highest.
33. The boiling point of 0.1 molal aqueous solution of urea is
(d) Vapour pressure of beaker B is lower than that of C and 100.18ºC at 1 atm. The molal elevation constant of water is
vapour pressure of beaker C is lower than that of A.
(a) 1.8 (b) 0.18
26. Vapour pressure of a pure liquid X is 2 atm at 300 K. It is
lowered to 1 atm on dissolving 1g of Y in 20g of liquid X. If (c) 18 (d) 18.6
molar mass of X is 200, what is the molar mass of Y ? 34. At certain hill-station, pure water boils at 99.725ºC. If Kb
–1
(a) 20 (b) 10 for water is 0.513ºC kg mol , the boiling point of 0.69m
(c) 100 (d) 30 solution of urea will be

27. The vapour pressure of benzene at a certain temp. is (a) 100.079ºC (b) 103ºC
640 mm Hg . A non-volatile-non-electrolyte solid weighing (c) 100.359ºC (d) unpredictable
2.175g is added to 39.0 g of benzene. The vapour pressure –1
35. The molal b.p. constant for water is 0.513ºC kg mol . When
of the solution is 600 mm Hg. What is the molecular weight
0.1 mole of sugar is dissolved in 200g of water, the solution
of the solid substance ?
boils under a pressure of 1 atm at
(a) 6.96 (b) 60
(a) 100.513ºC (b) 100.0513ºC
(c) 63.8 (d) none of the above
(c) 100.256ºC (d) 101.025ºC
28. The vapour pressure of solution of 5g of non-electrolyte
–2 36. An aqueous solution containing 1g of urea boils at 100.25ºC.
in 100 g of water at a particular temperature is 2985 Nm .
The aqueous solution containing 3g of glucose in the same
The vapour pressure of pure water at that temperature is
–2 volume will boil at
3000 Nm . The molecular weight of the solute is
(a) 100.75ºC (b) 100.5ºC
(a) 180 (b) 90
(c) 100ºC (d) 100.25ºC
(c) 270 (d) 200.
37. If the elevation in boiling point of a solution of 10gm of
29. Vapour pessure of CCl4 at 25ºC is 143 mm Hg. 0.5g of a non-
3 solute (mol. wt. = 100) in 100 gm of water is Tb , the
volatile solute (mol. wt. 65) is dissolved in 100 cm of CCl4.
ebullioscopic constant of water is
Find the vapour pressure of the solution. (Density of CCl4
3
= 1.58 g/cm ). (a) 10 (b) 10Tb
(a) 141.93 mm (b) 94.39 mm (c) Tb (d) Tb /10
(c) 199.34 mm (d) 143.99 mm
38. What weight of glycerol should be added to 600 g of water
30. A solution containing 12.5g of non-electrolyte substance
in order to lower its freezing point by 10º C ? (Kf = 1.86º C m–1).
in 185g of water shows boiling point elevation of 0.80 K.
(Molecular mass of glycerol is 92)
Calculate the molar mass of the substance.
(a) 496 g (b) 297 g
(Kb = 0.52 K kg mol–1)
SOLUTIONS 37
(c) 310 g (d) 426 g substance.
39. Sprinkling of salt helps in clearing the snow covered roads (a) 1198 (b) 500
in hills. The phenomenon involved in the process is (c) 1200 (d) 1000
(a) lowering in vapour pressure of snow 47. Grapes placed in three beakers X, Y and Z containing
(b) depression in freezing point of snow different type of solutions are shown in figures.
(c) increase in freezing point of snow If beaker X contains water, Y and Z contain
(d) melting of ice due to increase in temperature by putting
salt.
40. A solution of 1.25g of non-electrolyte in 20g of water freezes
–1
at 271.94 K. If Kf = 1.86 K Kg mol , then the molecular
weight of the solute will be (Tfo  0º C) (a) Y-hypotonic solution, Z-hypertonic solution
–1 –1 (b) Y-hypertonic solution, Z-hypotonic solution
(a) 179.79g mol (b) 207.8g mol
–1 –1 (c) Y and Z-isotonic solution
(c) 209.6g mol (d) 109.6g mol
(d) Y and Z-hypotonic solutions
41. The amount of urea to be dissolved in 500 cc of water
48. Osmotic pressure of a solution containing 2g dissolved
(K = 1.86) to produce a depression of 0.186ºC in the freezing
point is protein per 300 cm3 of solution in 20 mm of Hg at 27ºC. The
molecular mass of protein is
(a) 0.3 gm (b) 3 gm
(c) 6 gm (d) 9 gm. (a) 6239.6g mol–1 (b) 12315.5 g mol–1

42. The molar freezing point constant for water is 1.86º C/m. If (c) 3692.1 g mol–1 (d) 7368.4 g mol–1
342g of cane sugar (C12H22O11) is dissolved in 1000 g of 49. The osmotic pressure of a solution can be increased by
water, the solution will freeze at
(a) increasing the volume
(a) –1.86º (b) 1.86ºC
(b) increasing the number of solute molecules
(c) –3.92ºC (d) 2.42ºC
(c) decreasing the temperature
43. Pure benzene freezes at 5.45ºC at a certain place but a 0.374m
(d) removing semipermeable membrane.
solution of tetrachloroethane in benzene freezes at 3.55ºC.
The Kf for benzene is 50. Sea water is desalinated to get fresh water by which of the
–1 –1 following methods ?
(a) 5.08 K kg mol (b) 508 K kg mol
–1 –1 (a) When pressure more than osmotic pressure is applied
(c) 0.508K kg mol (d) 50.8ºC kg mol
pure water is squeezed out of sea water by reverse osmosis.
44. If 15 gm of a solute in 100 gm of water makes a solution that
(b) When excess pressure is applied on sea water pure
freezes at –1.0ºC, then 30 gm of the same solute in
water moves in by osmosis.
100 gm of water will make a solution that freezes at
(c) Water moves out from sea water due to osmosis.
(a) –0.5ºC (b) –2.0ºC
(d) Salt is precipitated from sea water when kept
(c) 0ºC (d) 2.0ºC
undisturbed for sometime.
45. An aqueous solution of a non-electrolyte solute boils at
51. Osmotic pressure is generally preferred for determining
100.52º C. The freezing point of the solution will be (Kf =
–1 –1 the molecular masses of protein because
1.86 K Kg mol , Kb = 0.52 K kg mol )
(a) it is difficult to find out mole fraction of protein for
(a) 0ºC (b) –1.86ºC
calculations by other methods
(c) 1.86ºC (d) None of the above.
(b) at elevated temperature the proteins are likely to
46. A solution is made by dissolving 20g of a substance in decompose and osmotic pressure is measured around room
500 mL of water. Its osmotic pressure was found to be temperature
600mm of Hg at 15ºC. Find the molecular weight of the
(c) the apparatus involved in finding out osmotic pressure
is simpler than other methods
SOLUTIONS 38

(d) it is easy to boil or freeze a solution containing proteins. 59. What will be the degree of dissociation of 0.1 M Mg(NO3)2
52. What will be the osmotic pressure in pascals exerted by a solution if van’t Hoff factor is 2.74 ?
solution prepared by dissolving 1.0g of polymer of molar (a) 75% (b) 87%
mass 150,000 in 500 mL of water at 37ºC ? (c) 100% (d) 92%
(a) 30.96 Pa (b) 34.36 Pa 60. The van’t Hoff factor of 0.005 M aqueous solution of KCl
(c) 68.72 Pa (d) 48.25 Pa is 1.95. The degree of ionisation of KCl is
Van’t Hoff Factor and Its Significance (a) 0.95 (b) 0.97
53. Which of the following will have same value of van’t Hoff (c) 0.94 (d) 0.96
factor as that of K4 [Fe (CN)6] ? 61. For which of the following solutes the van’t Hoff factor is
(a) Al2(SO4)3 (b) AlCl3 not greater than one ?
(a) NaNO3 (b) BaCl2
(c) Al(NO3)3 (d) Al(OH)3
54. A solute X when dissolved in a solvent associated to form (c) K4[Fe(CN)6] (d) NH2CONH2
a pentamer. The value of van’t Hoff factor (i) for the solute 62. The elevation in boiling point of a solution of 9.43g of
will be MgCl2 in 1 kg of water is (Kb = 0.52 K kg mol–1, Molar mass
(a) 0.5 (b) 5 of MgCl2=94.3g mol–1)
(c) 0.2 (d) 0.1 (a) 0.156 (b) 0.52
55. Why is the molecular mass determined by measuring (c) 0.17 (d) 0.94
colligative property in case of some solutes abnormal ?
Numeric Type Questions
(a) Due to association or dissociation of solute molecules.
63. To neutralize completely 20 mL of 0.1 M aqueous solution
(b) Due to insolubility of solute molecules.
of phosphorous acid (H3PO3), the volume of 0.1 M aqueous
(c) Due to decomposition of solute molecules. solution of KOH required in mL is
(d) Due to large size of solute molecules. 64.
20
6.02 × 10 molecules of urea are present in 100 ml of its
56. Which of the following has the highest freezing point ? solution. The concentration of urea is
(a) 1m NaCl solution (b) 1m KCl solution –1
65. Kf for water is 1.86 K kg mol . If your automobile radiator
(c) 1m AlCl3 solution (d) 1m C6H12O6 solution holds 1.0 kg of water, how many grams of ethylene glycol
(C2H6O2) must you add to get the freezing point of the
57. What amount of CaCl2 (i = 2.47) is dissolved in 2 litres of
solution lowered to –2.8ºC ?
water so that its osmotic pressure is 0.5 atm at 27ºC ?
66. A 5.25% solution of a substance is isotonic with a 1.5%
(a) 3.42 g (b) 9.24 g –1
solution of urea (molar mass = 60 g mol ) in the same
(c) 2.834 g (d) 1.825 g
solvent. If the densities of both the solutions are assumed
58. Which of the following statements is not correct ? –3
to be equal to 1.0 g cm , molar mass of the substance in g/
(a) Osmotic pressure () of a solution is given by the mol will be
relation  = MRT where M is the molarity of the solution.
67. The elevation in boiling point of a solution of 13.44 g of
(b) The correct order of osmotic pressure for 0.2 M aqueous –1
CuCl2 (Molecular weight = 134.4, Kb = 0.52 K molarity ) in
solution of each solute is CaCl2 > NaCl > CH3COOH >
1 kg water using the following information will be
glucose.
68. A 5.2 molal aqueous solution of methyl alcohol, CH3OH, is
(c) Two solutions of sucrose of same molality prepared in
supplied. What is the mole fraction of methyl alcohol in
different solvents will have same elevation boiling point.
the solution ?
(d) Relative lowering in vapour pressure of a solution
containing non-volatile solute is directly proportional to
mole fraction of solute.
SOLUTIONS 39

69. A mixture of ethyl alcohol and propyl alcohol has a vapour 74. If sodium sulphate is considered to be completely
pressure of 290 mm at 300K. The vapour pressure of pure dissociated into cations and anions in aqueous solution,
propyl alcohol is 200 mm. If the mole fraction of ethyl alcohol the change in freezing point of water in K (Tf), when 0.01
is 0.6, its pure component vapour pressure (in mm) at the mole of sodium sulphate is dissolved in 1 kg of water, is
–1
same temperature will be (kf = 1.86 K Kg mol )
70. Density of a 2.05 M solution of acetic acid in water is 1.02g/ 75. Benzene and toluene form nearly ideal solutions. At 20ºC,
mL. The molality of the solution is the vapour pressure of benzene is 75 Torr and that of toluene
71. The density of a solution prepared by dissolving 120g of is 22 Torr. The partial vapour pressure of benzene at 20ºC
urea (mol. mass = 60 u) in 1000 g of water is 1.15g/ml. The for a solution containing 78 g of benzene and 46 g of toluene
molarity of this solution is in Torr is
72. The density in g/ml of a 3.60 M sulphuric acid solution
which is 29% H2SO4 (molar mass = 98 g/mol) by mass will be
73. In 0.2m aqueous solution of weak acid HX, the degree of
ionization is 0.3. Taking Kf for water as 1.85, the freezing
point of solution (in ºC) will be nearest to
SOLUTIONS 40

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTION

1. The solubility of N2 in water at 300 K and 500 torr partial (c) 0.325 (d) 0.486

pressure is 0.01 gL1 .The solubility (in gL1 ) at 750 torr 7. Two 5 molal solutions are prepared by dissolving a non-
electrolyte non-volatile solute separately in the solvents
partial pressure is : Online 2016 SET (1)
X and Y. The molecular weights of the solvents are MX
(a) 0.0075 (b) 0.015
3
(c) 0.02 (d) 0.005 and MY, respectively where M x  M Y The relative
4
2. 18 g glucose (C6H12O6) is added to 178.2 g water. The
lowering of vapour pressure of the solution in X is “m”
vapour pressure of water (in torr) for this aqueous solution
times that of the solution in Y. Given that the number of
is: (2016)
moles of solute is very small in comparison to that of
(a) 76.0 (b) 752.4 solvent, the value of “m” is :
(c) 759.0 (d) 7.6 Online 2018 SET (2)
3. The freezing point of benzene decreases by 0.45°C when
4 3
0.2 g of acetic acid is added to 20 g of benzene. If acetic (a) (b)
3 4
acid associates to form a dimer in benzene, percentage
association of acetic acid in benzene will be :
1 1
(c) (d)
(Kf for benzene = 5.12 K kg mol–1) (2017) 2 4
(a) 80.4% (b) 74.6% 8. For 1 molal aqueous solution of the following compounds,
(c) 94.6% (d) 64.6% which one will show the highest freezing point? (2018)
(a) [Co(H2O)4Cl2]Cl.2H2O
4. What quantity (in mL) of a 45% acid solution of a mono-
protic strong acid must be mixed with a 20% solution of (b) [Co(H2O)3Cl3].3H2O
the same acid to produce 800 mL of a 29.875% acid (c) [Co(H2O)6]Cl3
solution ? (2017) (d) [Co(H2O)5Cl]Cl2.H2O
(a) 320 (b) 325 9. The mass of a non-volatile, non-electrolyte solute (molar
(c) 316 (d) 330 mass =50 g mol-1) needed to be dissolved in 114 g octane
5. 5g of Na2SO4 was dissolved in x g of H2O. The change in to reduce its vapour pressure to 75 percent is :
freezing point was found to be 3.82°C. If Na2SO4 is 81.5% Online 2018 SET (3)
ionized, the value of x Online 2017 SET (1) (a) 37.5 g (b) 75 g
(Kf for water = 1.86°C kg mol–1) is approximately : (c) 16.6 g (d) 50 g

(molar mass of S = 32 g mol–1 and that of Na = 23 g mol–1) 10. The vapour pressures of pure liquids A and B are 400 and
600 mm Hg, respectively at 298 K. On mixing the two liquids,
(a) 15 g (b) 25 g the sum of their initial volumes is equal to the volume of
(c) 45 g (d) 65 g the final mixture. The mole fraction of liquid B is 0.5 in the
mixture. The vapour pressure of the final solution, the mole
6. A solution is prepared by mixing 8.5 g of CH2Cl2 and 11.95
fractions of components A and B in vapour phase,
g of CHCl3. If vapour pressure of CH2Cl2 and CHCl3 at 298
respectively are:
K are 415 and 200 mm Hg respectively, the mole fraction of (2019-04-08/Shift-1)
CHCl3 in vapour form is : Online 2017 SET (2)
(a) 500 mmHg, 0.4, 0.6 (b) 500 mmHg, 0.5, 0.5
–1
(Molar mass of Cl = 35.5 g mol )
(c) 450 mmHg, 0.5, 0.5 (d) 450 mmHg, 0.4, 0.6
(a) 0.162 (b) 0.675
SOLUTIONS 41
11. Liquid ‘M’ and liquid ‘N’ form an ideal solution. The vapour (c) 1.51 (d) 1.35
pressures of pure liquids ‘M’ and ‘N’ are 450 and 700
15. At room temperature, a dilute solution of urea is prepared
mmHg, respectively, at the same temperature. Then correct
by dissolving 0.60 g of urea in 360 g of water. If the vapour
statement is: (2019-04-09/Shift-1)
pressure of pure water at this temperature is 35 mmHg,
Calculate the lowering of vapour pressure will be in mm
( xM  Mole fraction of ‘M’ in solution;
of Hg. (molar mass of urea= 60 g mol-1)
(2019-04-10/Shift-1)
xN  Mole fraction of ‘N’ in solution;
(a) 0.027 mmHg (b) 0.031 mmHg

yM Mole fraction of ‘M’ in vapour phase; (c) 0.028 mmHg (d) 0.017 mmHg
16. 1 g of a non-volatile non-electrolyte solute is dissolved
in 100 g of two different solvents A and B whose
yN  Mole fraction of ‘N’ in vapour phase)
ebullioscopic constants are in the ratio of 1: 5. The ratio

XM yM Tb  A 
(a) X  y of the elevation in their boiling points,  B , is:
b  
N N

XM yM (2019-04-10/Shift-2)
(b) X  y (a) 5: 1 (b) 10: 1
N N

(c) 1: 5 (d) 1: 0.2

(c)  X M  y M    x N  YN  17. The mole fraction of a solvent in aqueous solution of a
solute is 0.8.The molality (in mol kg 1 ) of the aqueous
X M yM
(d) X  y solution is (2019-04-12/Shift-1)
N N

(a) 13.88  102 (b) 13.88  101

12. The osmotic pressure of a dilute solution of an ionic
compound XY in water is four times that of a solution of (c) 13.88 (d) 13.88 103
0.01 M BaCl2 in water. Assuming complete dissociation
18. A solution is prepared by dissolving 0.6g of urea (molar
of the given ionic compounds in water, the concentration mass = 60 g mo1-1) and 1.8 g of glucose ( molar mass = 180
of XY (in mol L1 ) in solution is (2019-04-09/Shift-1) g mo1-1) in 100 mL, of water at 27°C. The osmotic pressure
of the (R = 0.08206 L atm K-1 moI-1) solution is:
(a) 4 104 (b) 6 102 (2019-04-12/Shift-2)
(c) 16 104 (d) 4 102 (a) 8.2 atm (b) 1.64 atm
(c) 4.92 atm (d) 2.46 atm
13. Molal depression constant for a solvent is 19. Which one of the following statements regarding
1
4.0 K kg mol The depression in thefreezing point of the Henry’s law is not correct? (2019-01-09/Shift-1)

solvent for 0.03mol kg 1 solution K 2SO4 is: (a) Higher the value of KH at a given pressure, higher is
the solubility of the gas in liquids.
(Assume complete dissociation of the electrolyte)
(b) Different gases have different KH (Henry’s law
(2019-04-09/Shift-2)
constant) values at the same temperature.
(a) 0.12 K (b) 0.36 K
(c) The partial pressure of the gas in vapour phase is
(c) 0.18 K (d) 0.24 K
proportional to the mole fraction of the gas in the
14. What would be the molality of 20% (mass/mass) aqueous
solution.
solution of KI? (molar mass of KI  166g mol1 )
(d) The value of KH increases with increase of temperature
(2019-04-09/Shift-2)
and KH is function of the nature of the gas.
(a) 1.08 (b) 1.48
SOLUTIONS 42
20. A solution containing 62 g ethylene glycol in 250g water 26. 8 g of NaOH is dissolved in 18 g of H2O. Mole fraction
is cooled to –10°C. If Kf for water is 1.86 K kg mol-1, the of NaOH in solution and molality (in mol kg- 1) of the
amount of water (in g) separated as ice is: solution respectively are: (2019-01-12/Shift-2)
(2019-01-09/Shift-2)
(a) 0.2, 22.20 (b) 0.2, 11.11
(a) 48 (b) 32
(c) 0.167, 11.11 (d) 0.167, 22.20
(c) 64 (d) 16
27. Elevation in the boiling point for 1 molal solution of
21. Liquids A and B form and ideal solution in the entire glucose is 2 K. The depression in the freezing point for
composition range. At 350 K, the vapour pressures of pure 2 molal solution of glucose in the samesolvent is 2 K. The
A and pure B are 7  103 Pa and 12  103 Pa , respectively.. relation between Kb and Kf is :
The composition of the vapour in equilibrium with a (2019-01-10/Shift-2)
solution containing 40 mole percent of A at this (a) K b  1.5K f (b) K b  K f
temperature is (2019-01-10/Shift-1)
(c) K b  0.5K f (d) K b  2K f
(a) x A  0.37; x B  0.63 (b) x A  0.28; x B  0.72
28. The amount of sugar (C12H22O11) required to prepare 2 L of
(c) x A  0.4; x B  0.6 (d) x A  0.76; x B  0.24 its 0.1 M aqueous solution is: (2019-01-10/Shift-2)
22. The freezing point of diluted milk sample is found to be (a) 136.8 g (b) 17.1 g
0.2C , while it should have been 0.5C for pure milk. (c) 68.4 g (d) 34.2 g
How much water been added to pure milk to make the 29. The size of a raw mango shrinks to a much smaller size
diluted sample? (2019-01-11/Shift-1) when kept in a concentrated salt solution. Which one of
(a) 1 cup of water to 2 cups of pure milk the following process can explain this ?
(b) 3 cups of water to 2 cups of pure milk (2020-09-02/Shift-2)
(c) 1 cup of water to 3 cups of pure milk (a) Diffusion (b) Osmosis
(d) 2 cups of water to 3 cups of pure milk (c) Reverse osmosis (d) Dialysis
23. K2HgI4 is 40% ionised in aqueous solution. 30. Henry’s constant (in kbar) for four gases , ,  and  in
The value of its van’t Hoff factor (i) is:
water at 298 K is given below :
(2019-01-11/Shift-2)
(a) 1.6 (b) 1.8
(c) 2.0 (d) 2.2
24. Freezing point of a 4% aqueous solution of X is equal to
freezing point of 12% aqueoussolution of Y. If molecular (density of water = 103 kg m–3 at 298 K)
weight of X is A, then molecular weight of Y is: This table implies that : (2020-09-03/Shift-1)
(2019-01-12/Shift-1) (a) solubility of  at 308 K is lower than at 298 K.
(a) 3A (b) 2A (b) The pressure of a 55.5 molal solution of  is 250 bar.
(c) A (d) 4A (c)  has the highest solubility in water at a given
25. Molecules of benzoic acid (C6H5COOH) dimerise in pressure.
benzene. ‘w’ g of the acid dissolved in 30 g of benzene
(d) The pressure of a 55.5 molal solution of  is 1 bar..
shows a depression in freezing point equal to 2 K. If the
percentage association of the acid to form dimer in the 31. The mole fraction of glucose in C6 H12 O6 an aqueous
solution is 80, then w is:(Given that Kf = 5 K kg mol-1, binary solution is 0.1. The mass percentage of water in
Molar mass of benzoic acid = 122 g mol-1). it, to the nearest integer, is ………. .
(2019-01-12/Shift-2) (2020-09-03/Shift-1)
(a) 2.4g (b) 1.0g
(c) 1.5g (d) 1.8g
SOLUTIONS 43
32. The strengths of 5.6 volume hydrogen peroxide 37. The elevation of boiling point of 0.10 m aqueous CrCl3xNH3
(of density 1 g/mL) in terms of mass percentage and solution is two times that of 0.05 m aqueous CaCl2 solution.
molarity (M), respectively, are: The value of x is …………….. .
(Take molar mass of hydrogen peroxide as 34 g/mol). [Assume 100% ionisation of the complex and CaCl 2,
(2020-09-03/Shift-2) coordination number of Cr as 6, and that all NH3 molecules
(a) 0.85 and 0.5 (b) 0.85 and 0.25 are present inside the coordination sphere]

(c) 1.7 and 0.25 (d) 1.7 and 0.5 (2020-09-06/Shift-1)

33. If 250 cm3 of an aqueous solution containing 0.73 g of a 38. A set of solution is prepared using 180g of water as a
protein A is isotonic with one litre of another aqueous solvent and 10g of different non-volatile solutes A, B and
solution containing 1.65 g of a protein B, at 298 K, the C. The relative lowering of vapour pressure in the
ratio of the molecular masses of A and B is ……… × 10–2 presence of these solutes are in the order [Given, molar
(to the nearest integer). (2020-09-03/Shift-2) mass of A = 100g mol-1 ; B =200g mol-1 ; C =10,000g mol-1]
(2020-09-06/Shift-2)
34. At 300 K, the vapour pressure of a solution containing
1 mole of n-hexane and 3 moles of n-heptane is 550 mm of (a) A > C > B (b) B > C > A
Hg. At the same temperature, if one more mole of n-heptane (c) C > B > A (d) A > B > C
is added to this solution, the vapour pressure of the 39. At 35oC, the vapour pressure of CS2 is 512 mm Hg and that
solution increases by 10 mm of Hg. What is the vapour of acetone is 344 mm Hg. A solution of CS2 in acetone has
pressure in mm Hg of n-heptane in its pure state _____? a total vapour pressure of 600 mm Hg. The false statement
(2020-09-04/Shift-1) amongst the following is : (2020-01-07/Shift-1)
35. The osmotic pressure of a solution of NaCl is 0.10 atm and (a) CS2 and acetone are less attracted to each other than
that of a glucose solution is 0.20 atm. The osmotic pressure to themselves
of a solution formed by mixing 1 L of the sodium chloride
(b) heat must be absorbed in order to produce the solution
solution with 2 L of the glucose solution is x  10–3 atm.
at 35oC
x is _______. (nearest integer) (2020-09-04/Shift-2)
(c) Raoult’s law is not obeyed by this system
36. A solution of two components containing n1 moles of the
1st component and n2 moles of the 2 nd component is (d) a mixture of 100 mL CS2 and 100 mL acetone has a
prepared. M 1 and M 2 are the molecular weights of volume < 200 mL
component 1 and 2 respectively. If d is the density of the 40. Two open beakers one containing a solvent and the other
solution in g mL-1, C2 is the molarity and x2 is the mole containing a mixture of that solvent with a non-volatile
fraction of the 2nd component, then C2 can be expressed as solute are together sealed in a container. Over time:
: (2020-09-06/Shift-1) (2020-01-07/Shift-2)

dx1 (a) the volume of the solution and the solvent does not
(a) C2  M  x  M  M  change
2 2 2 1
(b) the volume of the solution increases and the volume
of the solvent decreases
1000x2
(b) C2  M  x  M  M  (c) the volume of the solution decreases and the volume
1 2 2 1
of the solvent increases
dx2 (d) the volume of the solution does not change and the
(c) C2  M  x  M  M  volume of the solvent decreases
2 2 2 1

1000dx2
(d) C2  M  x  M  M 
1 2 2 1
SOLUTIONS 44

41. A graph of vapour pressure and temperature for three constant of C6 H 6 , is 5.12 C/m)
different liquids X, Y and Z is shown below: (2021-02-24/Shift - 2)
48. 1 molal aqueous solution of an electrolyte A2 B3 is 60%.
The boiling point of the solution at 1 atm is______K.
(Rounded-off to the nearest integer)
[Given Kb for  H 2 O   0.52 K kg mol 1 ]
(2021-02-25/Shift - 1)
49. If a compound AB dissociates to the extent of 75% in an
aqueous solution, the molality of the solution which
shows a 25K rise in the boiling point of the solution is
The following inferences are made: ______molal. (2021-02-25/Shift - 2)
(A) X has higher intermolecular interactions compared toY 50. 224 mL of SO2(g) at 298 K and 1 atm is passed through 100
mL of 0.1 M NaOH solution The non-volatile solute
(B) X has lower intermolecular interactions compared toY produced is dissolved in 36 g of water. the lowering of
(C) Z has lower intermolecular interactions compared toY vapour pressure of solution (assuming the solution is
2
The correct inference(s)is/are: (2020-01-08/Shift-1)  
dilute) PHo O  24 mm of Hg is x  10
2
mm of Hg, the
(a) C (b) A value of x is ______. (integer answer)
(c) B (d) A and C (2021-02-26/Shift - 1)
42. The molarity of HNO3 in a sample which has density 1.4 g/ 51. When 12.2g of benzoic acid is dissolved in 100g of water,
mL and mass percentage of 63% is————— (Molecular the freezing point of solution was found to be
weight of HNO3= 63). (2020-01-09/Shift-1) –0.93ºC(Kf(H2O) = 1.86 K mol–1). The number (n) of
43. How much amount of NaCl should be added to 600 g of benzoic acid molecules associated (assuming 100%
water (ñ=1.00 g/mL) to decrease the freezing point of water association) is _______.
to -0.2°C? (2021-02-26/Shift - 2)
(The freezing point depression constant for water = 2 K 52. A 6.50 molal solution of KOH (aq.) has a density of
Kg mol–1) (2020-01-09/Shift-1)
1.89 g cm–3. The molarity of the solution is _____ mol
44. One litre of sea water (d =1.03g/cm3) contains 10.3 mg of O2
gas. Determine the concentration of O2 in ppm: dm–3. (Round off to the nearest integer).
(2020-01-09/Shift-2) [Atomic masses: K : 39.0 u; O : 16.0 u; H : 1.0 u]
45. 4.5g of compund A (MW = 90) was used to make 250 mL of
(2021-03-16/Shift - 1)
its aqueous solution. The molarity of the solution in M is
53. AB2 is 10% dissociated in water to A2+ and B–. The boiling
X  101 . The value of x is _______. (Rounded off to the point of a 10.0 molal aqueous solution of AB2 is _____ºC.
nearest integer) (2021-02-024/Shfit - 1) (Round off to the nearest integer).
46. When 9.45 g of ClCH2COOH is added to 500 mL of water,
its freezing point drops by 0.5oC. The dissociation constant [Given: molal elevation constant of water Kb = 0.5 K kg
mol–1 boiling point of pure water 100ºC].
of ClCH2COOH is x 10 3 . The value of x is_____.
(2021-03-16/Shift - 1)
(Rounded off to the nearest integer)
54. At 363K, the vapor pressure of A is 21 kPa and that of B is
K f  1.86 K kg mol 1  (2021-02-24/Shift - 1) 18 kPa. One mole and 2 moles of B are mixed. Assuming
  H 2O  
that this solution is ideal, the vapor pressure the mixture
47. C6 H 6 freezes at 5.5C . The temperature at which a is ______ kPa. (Round off to the nearest integer).
solution of 10g of C4 H10 in 200g of C6 H 6 freeze (2021-03-16/Shift - 2)
is______ C. (The molal freezing poing depression
SOLUTIONS 45
55. The oxygen dissolved in water exerts a partial pressure of pressure of 0.835 bar, then x mmol of CO2 would dissolve
20kPa in the vapour above water. The molar solubility of in 0.9 L of water. The value of x is ______. (Nearest integer)
oxygen in water is ________. (Henry’s law constant for CO2 at 298 K is 1.67 × 103 bar)
(Round off to the nearnes integer). (2021-07-25/Shift - 1)
(Given: Henry’s law constant = KH = 8.0 × 104kPa for O2. 63. When 3.00 g of a substance ‘X’ is dissolved in 100g of
Density of water with dissolved oxygen = 1.0 kg dm ) –3 CCl4, it raises the boiling by 0.60K. The molar mass of the
substance ‘X’ is ______ g mol–1. (Nearest integer).
(2021-03-17/Shift - 1)
[Given - Kb for CCl4 is 5.0 K kg mol–1]
56. The mole fraction of a solute in a 100 molal aqueous
(2021-07-25/Shift - 2)
solution is ______ × 10–2.
64. In a solvent 50% of an acid HA dimerizes and the rest
(Round off to the nearest integer).
dissociates. The Van’t Hoff factor of the acid is _____
[Given: Atomic mass: H : 1.0u, O : 16.0u] × 10–2. (Round off to the nearest integer)
(2021-03-17/Shift - 1) (2021-07-27/Shift - 2)
57. A 1 molal K4Fe(CN)6 solution has a degree of dissociation 65. 1.46g of a biopolymer dissolved in a 100 mL water at 300 K
of 0.4. Its boiling point is equal to that of another solution exerted an osmotic pressure of 2.42 × 10–3 bar. The molar
which contains 18.1 weight percent of a non electrolytic mass of the biopolymer is _______ × 104g mol–1
solute A. The molar mass of A is ______u. (Round off the (Round off to the nearest integer)
nearest integer). [Use: R = 0.083 L bar mol–1 K–1]
–3
[Density of water = 1.0 g cm ] (2021-07-27/Shift - 2)
(2021-03-17/Shift - 2) 66. Of the following four aqueous solutions, total number of
58. 1 molal solution of a weak acid HA has a freezing point of those solutions whose freezing point is lower than that of
3.885ºC. The degree of dissociation of this acid is _______ 0.10 m C2H5OH is ______. (Integer answer)
× 10-3. (Round off to the Nearest integer). (i) 0.10 m Ba3(PO4)2
[Given: Molal depression constant of water = 1.85 K kg (ii) 0.10 m Na2SO4
mol–1 Freezing point of pure water = 0ºC].
(iii) 0.10 m KCl
(2021-03-14/Shift - 1)
(iv) 0.10 m Li3PO4 (2021-8-26/Shift -1)
59. A solute a dimerizes in water. The boiling point of a 2 molal
solution of A is 100.52ºC. The percentage association of A 67. An aqueous KCl solution of density 1.20 g mL–1 has a
is ________ . (Round off to the nearest integer). molality of 3.30 mol kg–1. the molarity of the solution in mol
L–1 is _______ (nearest integer).
[Use: Kb for water = 0.52 K kg mol–1 boiling point of water
= 100ºC]. (2021-03-18/Shift - 2) [Molar mass of KCl = 74.5] (2021-8-26/Shift -1)
60. At 20ºC, the vapour pressure of benzene is 70 torr and 68. 83g of ethylene glycol dissolved in 625 g of water. The
that of methyl benzene is 20 torr. The mole fraction of freezing point of the solution is ______ K. (Nearest integer)
benzene in the vapour phase at 20ºC above an equimolar [Use: molal freezing point depression constant of water =
mixture of benzene and methyl benzene is ________ 1.86 K kg mol–1, Freezing point of water = 273 K, Atomic
×10 –2. (Nearest integer) (2021-07-20/Shift - 1) masses; C - 12.0 u, O - 16.0 u, H - 1.0 u]
61. The vapour pressures of A and B at 25ºC are 90 mm Hg (2021-8-26/Shift - 2)
and 15 mm Hg respectively. If A and B are mixed such that 69. 1 kg of 0.75 molal aqueous solution of sucrose can be
the mole fraction of A in the mixture is 0.6, then the mole cooled up to –4ºC before freezing. The amount of ice (in g)
fraction of B in the vapour phase is x × 10–1. The value of that will be separated out is ________. (Nearest integer)
x is _____. (Nearest integer) [Given: Kf(H2O) = 1.86 K kg mol–1]
(2021-07-20/Shift - 2) (2021-08-27/Shift - 1)
62. CO2 gas is bubbled through water during a soft drink
manufacturing process 298K. If CO2 exerts a partial
SOLUTIONS 46
70. 40g of glucose (Molar mass = 180) is mixed with 200 mL of 73. The water having more dissolved O2 is:
water. The freezing point of solution is ______ K. (Nearest (2021-07-08)
integer)
(a) Boiling water (b) Water at 80ºC
[Given: Kf = 1.86 K kg mol–1; Density of water = 1.00
(c) Polluted water (d) Water at 4ºC
g cm–3; Freezing point of water = 273.15 K]
74. Which one of the following 0.06 M aqueous solutions
(2021-08-27/Shift - 2)
has lowest freezing point? (2021-07-22/Shfit - 2)
71. 1.22g of an organic acid is separately dissolved in 100g of
(a) Al2(SO4)3
benzene (Kb = 2.6 K kg mol–1) and 100g of acetone (Kb = 1.7
K kg mol–1). The acid is known to dimerize in benzene but (b) C6H12O6
remain as a monomer is acetone. The boiling point of the (c) KI
solution in acetone increases by 0.17ºC. The increse in
(d) K2SO4
boiling point of solution in benzene in ºC is x ×10–2. The
value of x is _______. (Nearest interger) 75. Which one of the following 0.10 M aqueous solutions will
exhibit the largest freezing point depression?
[Atomic mass: C = 12.0, H = 1.0, O = 16.0]
(2021-08-31/Shift - 2) (2021-08-31/Shift - 1)

72. Given below are two statements: (a) Hydrazine (b) Glucose

Statement I: A mixture of chloroform and aniline can be (c) Glycine (d) KHSO4
separated by simple distillation.
Statement II: When separating aniline from a mixture of
aniline and water by steam distillation aniline boils below
its boiling point.
In the light of the above statements, choose the most
appropriate answer from the options given below.
(2021-02-26/Shift - 1)
(a) Both statement I and statement II are true.
(b) Both statement I and statement II are false.
(c) Statement I is false but statement II is true
(d) Statement I is true but statement II is false.
SOLUTIONS 47

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only one correct option] (b) shows no deviation from Raoult’s law
(c) show positive deviation from Raoult’s law
1. In a solution of 7.8 g of benzene (C6H6) and 46 g of
(d) is saturated
toluene (C6H5CH3), the mole fraction of benzene is
9. If P A is the vapour pressure of a pure liquid A and the
(a) 1/6 (b) 1/5 mole fraction of A in the mixture of two liquids A and B
(c) 1/2 (d) 1/3 is x, the partial vapour pressure of A is :
2. To 5.85 g of NaCl, one kg of water is added to prepare a (a) (1  x) PA (b) xPA
solution. What is the strength of NaCl in this solution ?
(Molecular weight of NaCl = 58.5) x 1 x
(a) 0.1 Normal (b) 0.1 Molal (c) (1  x) PA (d) PA
x
(c) 0.1 Molar (d) 0.1 Formal
10. Air contains O2 and N2 in the ratio of 1 : 4. The ratio of
3. The formula weight of H2SO4 is 98. The weight of the their solubilities in terms of mole fractions at atmospheric
acid in 400 ml of 0.1 M solution is pressure and room temperature will be (Given Henry’s
7 7
(a) 2.45 g (b) 3.92 g constant for O2 = 3.30 × 10 torr, for N2 = 6.60 × 10 torr)
(c) 4.90 g (d) 9.8 g (a) 1 : 2 (b) 2 : 1
4. The molarity of a solution of Na2CO3 having 10.6 g in (c) 4 : 1 (d) 1 : 4
500 ml of solution is 11. The relative lowering of the vapour pressure is equal to
(a) 0.2 M (b) 2 M the ratio between the number of
(c) 20 M (d) 0.02 M (a) solute molecules to the solvent molecules
5. Molarity of a solution containing 1g NaOH in 250 ml of (b) solute molecules to the total molecules in the solution
solution is (c) solvent molecules to the total molecules in the
(a) 0.1 M (b) 1 M solution
(c) 0.01 M (d) 0.001 M (d) solvent molecules to the total number of ions of the
solute
6. Raoult's law states that for a dilute solution,
12. Vapour pressure of a solution of non-volatile solute is
(a) the lowering of vapour pressure is equal to the mole
fraction of the solute (a) directly proportional to the mole fraction of the
solvent
(b) the relative lowering of vapour pessure is
proprotional to the amount of solute in the solution (b) Independent of mole fraction of the solute
(c) the relative lowering of vapour pressure is equal to (c) inversely proportional to the mole fraction of the
the mole fraction of the solute solvent
(d) the vapour pressure of the solution is equal to the (d) directly proportional to the mole fraction of the solute
mole fraction of the solvent 13. Vapour pressure of a solution of 5 g of non-electrolyte
7. Which of the following pairs shows a negative deviation in 100 g of water at a particular temperature is 2985 N/
from Raoult's law ? m2. The vapour pressure of pure water is 3000 N/m2, the
(a) Acetone–benzene (b) Acetone–ethanol molecular weight of the solute is
(c) Acetone–chloroform (d) Benzene–methanol (a) 60 (b) 120
8. An azeotropic solution of two liquids has boiling point (c) 178.2 (d) 380
lower than either of them when it
(a) shows negative deviation from Raoult’s law
SOLUTIONS 48
14. The vapour pressure of benzene at a certain temperature respectively
is 640 mm of Hg. A nonvolatile electrolyte solute (a) greater than 1 and greater than 1
weighing 2.175 g is added to 30.08 g of benzene. If the
(b) less than 1 and greater than 1
vapour pressure of the solution is 600 mm of Hg, what is
the molecular weight of the solid substance ? (c) less than 1 and less than 1

(a) 79.82 (b) 84.46 (d) greater than 1 and less than 1

(c) 59.60 (d) 49.50 22. Which one has the highest boiling point ?

15. Elevation in boiling point was 0.52ºC when 6 gm of a (a) 0.1 N Na2SO4 (b) 0.1 N MgSO4
compound X was dissolved in 100 gm of water. Molecular (c) 0.1 M Al2(SO4)3 (d) 0.1 M BaSO4
weight of X is (Kb of water is 0.52 K-kg/mol) 23. Which of the following aqueous solutions has the
(a) 120 (b) 60 highest boiling point ?
(c) 600 (d) 180 (a) 0.1 M KNO3 (b) 0.1 M Na3PO4
–1
16. The molal b.p. constant for water is 0.513ºC kg mol . (c) 0.1 M BaCl2 (d) 0.1 M K2SO4
When 0.1 mole of sugar is dissolved in 200 g of water,
24. The freezing point of equimolal aqueous solutions will
the solution boils under a pressure of 1 atm at
be highest for
(a) 100.513ºC kg/mol (b) 100.0513ºC kg/mol
(a) C6H5NH3Cl (aniline hydrochloride)
(c) 100.256ºC kg/mol (d) 101.025ºC kg/mol
(b) Ca(NO3)
17. The freezing point of a 0.05 molal solution of a non-
electrolyte in water is (c) La (NO3)3

(a) –1.86ºC (b) –0.93ºC (d) C6H12O6 (glucose)

(c) –0.093ºC (d) 0.93ºC 25. 0.01 M solution each of urea, common salt and Na2SO4
are taken, the ratio of depression of freezing point is
18. Calculate the molecular weight of a substance if the
freezing point of a solution containing 100 g of benzene (a) 1 : 1 : 1 (b) 1 : 2 : 1
and 0.2g of the substance is 0.17 K below that of (c) 1 : 2 : 3 (d) 2 : 2 : 3
benzene. The cryoscopic constant of benzene is 5.16 K 26. The osmotic pressures of equimolar solutions of
kg mol–1. Al2(SO4)3, KCl and sugar will be in the order
(a) 70.46 (b) 85.66
(a) KCl < Al2(SO4)3< sugar
(c) 60.23 (d) 178.25
(b) sugar < KCl < Al2 (SO4)3
19. Which statement is incorrect about osmotic pressure
(), volume (V) and temperature (T) ? (c) sugar > KCl > Al2 (SO4)3
(a) 1/V when T is constant. (d) KCl < sugar < Al2 (SO4)3
(b) T when V is constant. 27. The freezing point of 1 molal NaCl solution assuming
(c)  V when T is constant. NaCl to be 100% dissociated in water is
(d) V is constant when T is constant. (a) –1.86ºC (b) –3.72ºC
20. A plant cell shrinks when it is kept in (c) +1.86ºC (d) +3.72ºC
(a) Hypotonic solution 28. The molal freezing point constant for water is 1.86ºC/
(b) A hypertonic solution mole. Therefore, the freezing point of 0.1M NaCl solution
(c) A solution isotonic with cell sap in water is expected to be
(d) Water. (a) –1.86ºC (b) –0.186ºC
21. The van't Hoff factors i for an electrolyte which (c) –0.372ºC (d) +0.337ºC
undergoes dissociation and association in solvents are
SOLUTIONS 49
29. When 1.345 g of CuCl2 is dissolved in 1 kg of water, the deviations from Raoult's law.
elevation in boiling point will be (Kb = 0.52, molar mass (b) A solution in which heat is absorbed shows negative
of CuCl2 = 134.5) deviations from Raoult's law.
(a) 0.05 (b) 0.30 (c) When one component in solution shows negative
deviation from Raoult's law, the other exhibits positive
(c) 0.15 (d) 0.015
deviation.
30. Which one of the following solutions of sulphuric acid
(d) When one component in solution shows positive
will exactly neutralise 25 ml of 0.2 M sodium hydroxide
deviation from Raoult's law, so does the other.
solution ?
37. Which statement about the composition of vapour over
(a) 12.5 ml of 0.1 M solution
an ideal 1 : 1 molar mixture of benzene and toluene is correct?
(b) 25 ml of 0.1 M solution Assume the temperature is constant at 25ºC.
(c) 25 ml of 0.2 M solution Vapour pressure data (25ºC) :
(d) 50 ml of 0.2 M solution Benzene 75 mm Hg
31. The normality of 10% (weight/volume) acetic acid is Toluene 22 mm Hg
(a) 1 N (b) 10 N (a) The vapour will contain higher percentage of
(c) 1.7 N (d) 0.83 N benzene
32. 30 ml of solution is neutralised by 15 ml of 0.2 N base. (b) The vapour will contain higher percentage of
The strength of the acid solution is toluene
(a) 0.1 N (b) 0.15 N (c) The vapour will contain equal amount of benzene
(c) 0.3 N (d) 0.4 N and toluene
(d) Not enough information is given to make a
33. 10 ml of 3N-HCl, 20 ml of N/2 H2SO4 and 30 ml of N/3
prediction
HNO3 are mixed together and volume made to one litre.
38. 100 ml of a liquid A was mixed with 25 ml of a liquid B to
The normality of the resulting solution is
give a non-ideal solution of A-B mixture. The volume of
(a) N/2 (b) N/10 this mixture would be
(c) N/20 (d) N/40 (a) 75 ml (b) 125 ml
34. 50 ml of 0.2 N HCl, 50 ml of 0.1 N H2SO4 and 100 ml 0.2 (c) close to 125 ml (d) just more than 125 ml
N HNO3 are mixed. The normality of resulting solution 39. The diagram given below is a vapour pressure-
is composition diagram for a binary solution of A and B. In
(a) 0.10 N (b) 0.15 N the solution, A–B interactions are
(c) 0.175 N (d) 0.20 N (a) similar to A–A and B–B interactions
35. A solution is prepared containing a 2 : 1 mol ratio of (b) greater than A–A and B–B interactions
dibromo ethane (C 2 H 4Br 2) and dibromo propane (c) smaller than A–A and B–B interactions
(C3H6Br2) what is the total vapour pressure over the (d) unpredictable.
solution assuming ideal behaviour ?
Vapour pressure (mm Hg)
C2H4Br2 173
C3H6Br2 127
(a) 300 mm Hg (b) 158 mm Hg
(c) 150 mm Hg (d) 142 mm Hg
36. Which of the following statements is correct for a binary
solution ?
(a) A solution in which heat is evolved exhibits positive
SOLUTIONS 50
40. Mixture of volatile components A and B has total vapour
(d) liquid solute, solid solvent
pressure (in torr) :
46. On freezing an aqueous solution of sugar, the solid that
P = 254 – 119XA
starts separating out is
where, XA is mole fraction of A in mixture. Hence
(a) sugar (b) ice
p0A and p0B are (in torr) : (c) solution with the same composition
(a) 254, 119 (b) 119, 254 (d) solution with a different composition.
(c) 135, 254 (d) 154, 119 47. Given that Tf is the depression in freezing point of the
41. The millimoles of N2 gas that will dissolve in 1L of water solvent in a solution of a non volatile solute of molality
at 298 K. when it is bubbled through water and has a
 T f 
partial pressure of 0.96 bar will be 1, the quantity lim   is equal to
m 1
 m 
(Given that at 298 K KH = 76.8 k bar)
(a) 0.59 (b) 0.69 (a) Lf (latent heat of fusion)
(c) 0.79 (d) 0.89 (b) Kb (ebullioscopic constant)
42. Consider the following statements (c) Kf (cryoscopic constant)
1. Isotonic solutions have the same molar concentration
(d) Hfus (enthalpy of fusion)
at a given temperature.
48. 10 g of glucose (1), 10 g of urea (2) and 10 g of sucrose
2. The molal elevation constant Kb is characteristic of a
solvent, and is independent of the solute added. (3) are dissolved in 250 mL of water at 300 K ( = osmotic
pressure of solution). The relationship between the
3. The freezing point of a 0.1 M aqueous KCl solution is
osmotic pressure of the solutions is
more than that of a 0.1 M aqueous AlCl3 solution.
(a) 1 > 2 > 3 (b) 3 > 1 > 2
Which of these statements is correct.
(c) 2 > 1 > 3 (d) 2 > 3 > 1
(a) 1 and 2 (b) 2 and 3
(c) 1 and 3 (d) 1, 2 and 3 49. Which of the following pairs of solutions is isotonic ?
(a) 6% urea and 6% glucose (w/v)
43. An aqueous solution freezes at –2.550C. What is its
(b) 18% urea and 18% glucose (w/v)
boiling point ( K b of water  0.52 K / m; K f of water
(c) 6% urea and 18% fructose (w/v)
 1.86 K / m) ? (d) 34.2% sucrose and 60% glucose (w/v)
0 0 50. Two aqueous solutions S1 and S2 are separated by a
(a) 107.0 C (b) 100.6 C
semi-permeable membrane. S2 has lower vapour pressure
(c) 100.10C (d) 100.70C
than S1. Then
44. The normal boiling point of toluene is 110.70C, and its
(a) More solvent will flow from S1 to S2
boiling point elevation constant is 3.32 K kg mol–1. The
enthalpy of vapourization of toluene is nearly (b) More solvent will flow from S2 to S1

(a) 17.0 kJ mol–1 (b) 34.0 kJ mol–1 (c) Solvent from S1 and S2 will flow at equal rates
(d) No flow will take place.
(c) 51.0 kJ mol–1 (d) 68.0 kJ mol–1
51. If a solute undergoes dimerization and trimerization, the
45. During depression of freezing point in a solution the
minimum values of the van't Hoff factors are
following are in equilibrium
(a) 0.50 and 1.50 (b) 1.50 and 1.33
(a) liquid solution, solid solvent
(c) 0.50 and 0.33 (d) 0.25 and 0.67
(b) liquid solvent, solid solute
(c) liquid solute, solid solute
SOLUTIONS 51
52. Solutions A, B, C and D are respectively 0.1 M glucose, Objective Question II
0.05 M NaCl, 0.05 M BaCl2 and 0.1 M AlCl3. Which of
[One or more than one correct option]
the following pairs is isotonic ?
58. The solution showing positive deviation
(a) A and B (b) B and C
(a) have V (mixing) = + ve
(c) A and D (d) A and C
(b) have H (mixing) = – ve
53. Among 0.1 M solutions of urea, Na3PO4 and Al2 (SO4)3,
(c) form minimum boiling azeotropes.
which is incorrect ?
(d) have lower vapour pressure of each component in
(a) the vapour pressure and freezing point are the lowest
the solution than their pure vapour pressure.
for urea
59. Which pair (s) of liquids on mixing are expected to show
(b) the vapour pressure and freezing point are the
no net volume change and no heat effect
highest for urea
(a) acetone and ethanol
(c) the boiling point is the highest for Al2(SO4)3
(b) chlorobenzene and bromobenzene
(d) the depression in freezing point is the highest for
(c) chloroform and benzene
Al2(SO4)3
(d) n-butyl chloride and n-butyl bromide.
54. Which of the following graphs represent the behaviour
of ideal binary liquid mixture ? 60. Which of the following is/are correct statements (s) about
the Raoult’s law applied to a solution of non-volatile
(a) Plot of 1/PTotal against yA is linear solute ?
(b) Plot of 1/PTotal against yB is non-linear (a) Vapour pressure of solution is proportional to mole
(c) Plot of PTotal against yA is linear fraction of solute

(d) Plot of PTotal against yB is linear (b) V.P. of solution is proportional to the mole fraction of
solvent
1 1 (c) Relative lowering of V.P. = mole fraction of solute
55. The plot of y against x is linear with slope and
A A (d) Relative lowering of vapour pressure is proportional
intercept respectively : to the mole fraction of solute.
61. In binary liquid mixture of components, A and B, the
PA0 PA0  PB0 PA0 PB0  PA0
(a) 0 and (b) 0 and former has greater tendency to escape into the vapour
PB PB0 PB PB0 state than demanded by Raoult’s law. Indicate the correct
statement(s)
PB0 PA0  PB0 PB0 PB0  PA0 (a) Component A shows positive deviation and the
(c) 0 and (d) 0 and
PA PA0 PA PB0 component B negative deviation

56. 0.2 molal acid HX is 20% ionised in solution. Kf = 1.86 K (b) Both components show positive deviations
–1
Kg mol . The freezing point of the solution is : (c) Component A shows negative deviation and the
component B positive deviation

(a) – 0.45 (b) – 0.90 (d) The component B has also greater tendency to
escape into the vapour state than demanded by Raoult’s
(c) – 0.31 (d) – 0.53
law
57. 0.004 M Na2SO4 is isotonic with 0.01 M glucose. The 62. Colligative properties of a solution are
degree of dissociation of Na2SO4 is
(a) independent of the nature of solute
(a) 75% (b) 50% (b) inversely proportional to molecular mass of solute
(c) 25% (d) 85% (c) Proportional to concentration of solute
(d) independent of the amount of solvent.
SOLUTIONS 52
63. In the depression in freezing point experiment, it is Numeric Value Type Questions
observed that
67. When 1.0 g of urea is dissolved in 200 g of an unknown
(a) the vapour pressure of the solution is less than that solvent X, the X freezing point is lowered by 0.25ºC.
of pure solvent. When 1.5g of an unknown, non-electrolytic solute Y is
(b) the vapour pressure of the solution is more than that dissolved in 125 g of same solvent X, freezing point is
of pure solvent lowered by 0.2 ºC and vapour pressure is lowered by
(c) only solute molecules solidify at the freezing point 1%. If freezing point of X, is 12ºC, determine molar
enthalpy of fusion of X in kJ.
(d) only solvent molecules solidify at the freezing point.
68. A non-volatile organic compound X was used to make-
64. A binary liquids mixture of two liquid A and B showing
up two solution. Solution A contains 5.0 g of X in 100 g
the departure from the ideal behaviour :
of water and solution B contains 2.0 g of X in 100 g of
(a) behaves as an ideal solution of B into A when XB0 benzene. Solution A has vapour pressure of 754.5 mm of
(b) behaves as an ideal solution of A into B when XA0 Hg at normal boiling point of water and solution B has
the same vapour pressure at the normal boiling point of
(c) HSol’n is always positive benzene. Assuming X undergo partial dimerization in
(d) TSSol’n is always positive benzene, determine percentage of X dimerized in benzene
solution.
65. Composition of an azeotrope
69. A mixture of NaCl and sucrose of combined mass 10.2 g
(a) is independent of external pressure because it is a is dissolved in enough water to make up a 250 mL
compound solution. The osmotic pressure of the solution is 7.32
(b) alters on changing the external pressure atm at 23ºC. Calculate the mass percentage of NaCl in
(c) remains unchanged during distillation at a constant the mixture.
external pressure Assertion Reason
(d) fluctuates even at constant pressure
(A) If both Assertion and Reason are correct
66. Study the figure given aside and pick out the correct and Reason is the correct explanation of
option(s) of the following :
Assertion.
(B) If both Assertion and Reason are true but
Reason is not the correct explanation of
Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
70. Assertion (A) : The sum of mole fractions of all
components of a solution is unity.
Reason (R) : Mole fraction is independent of
(a) A white precipitate of AgCl is formed on AgNO3 side temperature.
(b) A white precipitate of AgCl is formed on BaCl2 side (a) A (b) B
(c) No precipitate is formed on either side (c) C (d) D
(d) Meniscus of BaCl2 solution rises and that of AgNO3 71. Assertion (A) : Hmix and Vmix are zero for the ideal
solution falls in due course of time solution.
Reason (R) : The interactions between the particle of
the components of a solution are almost identical as
between particles in the liquids.
(a) A (b) B
(c) C (d) D
SOLUTIONS 53

72. Assertion (A) : The vapour pressure of a liquid 76. Mn = Normal molecular mass of solute
decreases if some non-volatile solute is dissolved in it.
Mo = Observed molecular mass of solute from colligative
Reason (R) : The relative lowering of vapour pressure property measurement
of a solution containing a non-volatile solute is equal to
Match the following :
the mole fraction of the solute in the solution.
Column - I Column - II
(a) A (b) B
(c) C (d) D (A) Mo < Mn (P) 0.1 M CH3COOH
73. Assertion (A) : NaCl in water and organic acids in is benzene
benzene show abnormal molecular mass (B) Mo  Mn/3 (Q) 0.1 M urea in water
Reason (R) : Abnormal molecular mass is obtained when
the substance in the solution undergoes dissociation (C) Mo > Mn (R) 0.05 M barium chloride in
or association. water
(a) A (b) B (D) Mo = Mn (S) 0.1 M CH3COOH in water
(c) C (d) D 77. Hf = Molar heat of fusion of ice ; Lf = Latent heat of
74. Assertion (A) : If more and more non-volatile solute is –1
fusion of ice (g )
added to a solvent, the freezing point of the solution
keeps on reducing. Hv = Molar heat of vaporisation of water ; Lv = Latent
–1
Reason (R) : Presence of large amount of the solid solute heat of vaporisation of water (g )
does not allow the solution to freeze. Match the following appropriately
(a) A (b) B Column - I Column - II
(c) C (d) D
18  373  373  R
75. Assertion (A) : The boiling point of 0.1 M urea solution (A) Molal depression (P)
1000H v
is less than that of 0.1 M KCl solution.
Reason (R) : Elevation of boiling point is directly constant of water
proportional to the number of species present in the
solution. 373  373  R
(B) Molal elevation (Q) 1000 L v
(a) A (b) B
(c) C (d) D constant of water

Match the Following 18  273  273  R

(C) Tf of solution (R)
Each question has two columns. Four 1000 H f
options are given representing matching of containing 9.0 g of
elements from Column-I and Column-II. glucose in 50g of water
Only one of these four options corresponds
to a correct matching.For each question, 273  273  R
(D) Tb of solution (S) 1000 L f
choose the option corresponding to the
correct matching. containing 3.0g of
urea in 50 g of water
SOLUTIONS 54

Paragraph Type Questions

Use the following passage, solve Q. 78 to Q. 80
Passage
A Protein has been isolated as sodium salt with their
molecular form Na 2 P (this notation means xNa  ions are
associated with a negatively charged protein P  x ). A
solution of this salt was prepared by dissolving x y
of this sodium salt of protein in 10g of water and
ebullioscopic analysis revealed that solution boils at
temperature 6.78×10-3 o C higher than the normal

boiling point of pure water. K b of water of

0.52k kg mol1 . Also elemental analysis revealed that

the salt contain 1% sodium metal by weight.
78. Deduce molecular formula of protein.
(a) NaP (b) Na2P
(c) Na4P (d) Na5P
79. Determine molecular weight of sodium salt of protein.
(a) 2300 (b) 4600
(c) 9200 (d) 11500
80. Determine molecular weight of acidic form of protein :
(a) 11390 (b) 2278
(c) 9112 (d) 4556
SOLUTIONS 55

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

3 –3
1. To 500 cm of water, 3.0 × 10 kg of acetic acid is added. If 8. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g of
23% of acetic acid is dissociated, what will be the –1
benzene (Kf = 1.72 K kg mol ), a freezing point depression of
depression in freezing point? Kf and density of water are
–1 –1 –3 2K is observed. The Van’t Hoff factor (i) is (2007)
1.86 K kg mol and 0.997 g cm , respectively. (2000)
(a) 0.5 (b) 1
2. During depression of freezing point in a solution the
following are in equilibrium (2003) (c) 2 (d) 3

(a) liquid solvent, solid solvent Comprehension-I

(b) liquid solvent, solid solute Properties such as boiling point, freezing point and vapour
pressure of a pure solvent change when solute molecules
(c) liquid solute, solid solute
are added to get homogeneous solution. These are called
(d) liquid solute, solid solvent colligative properties. Applications of colligative
3. Consider the three solvents of identical molar masses. properties are very useful in day-to-day life. One of its
Match their boiling point with their kb values (2003) examples is the use of ethylene glycol and water mixture
Solvents Boiling point kb values as anti-freezing liquid in the radiator of automobiles.

X 100ºC 0.92 A solution M is prepared by mixing ethanol and water.

The mole fraction of ethanol in the mixture is 0.9
Y 27ºC 0.63
Given, Freezing point depression constant of water
Z 283ºC 0.53
4. 0.004 M Na2SO4 is isotonic with 0.01 M glucose. Degree (k fwater )=1.86K kg mol-1
of dissociation of Na2SO4 is (2004) Freezing point depression constant of ethanol
(a) 75% (b) 50%
(k ethanol
f )=2.0K kg mol-1
(c) 25% (d) 85%
Boiling point elevation constant of water
5. 1.22 g of benzoic acid is dissolved in 100 g of acetone and
100 g of benzene separately. Boiling point of the solution (k water )=0.52K kg mol -1
b
in acetone increases by 0.17ºC, while that in the benzene
increases by 0.13ºC; Kb for acetone and benzene is 1.7 K Boiling point elevation constant of ethanol
–1 –1
Kg mol and 2.6 K kg mol respectively. Find molecular (k ethanol )=1.2K kg mol -1
b
weight of benzoic acid in two cases and justify your
answer. (2004) Standard freezing point of water = 273 K
6. The elevation in boiling point of a solution of 13.44g of Standard freezing point of ethanol = 155.7 K
CuCl2 in 1 kg of water using the following information will
Standard boiling point of water = 373 K
b e ( M o l e cu la r weight of CuCl 2 = 134.4 and
–1 Standard boiling point of ethanol = 351.5 K
Kb = 0.52 K molal ) (2005)
(a) 0.16 (b) 0.05 Vapour pressure of pure water = 32.8 mm Hg

(c) 0.1 (d) 0.2 Vapour pressure of pure ethanol = 40 mm Hg

7. 75.2 g of C6H5OH (phenol) is dissolved in 1kg of solvent
of kf = 14. If the depression in freezing point is 7K, then Molecular weight of water = 18 g mol1
find the percentage of phenol that dimerises. (2006)
SOLUTIONS 56
14. For a dilute solution containing 2.5g of a non-volatile non-
Molecular weight of ethanol = 46g mol1
electrolyte solute in 100g of water, the elevation in boiling
In answering the following questions, consider the point at 1 atm pressure is 2ºC. Assuming concentration of
solutions to be ideal dilute solutions and solutes to be solute is much lower than the concentration of solvent,
non-volatile and non-dissociative. (2008) the vapour pressure (mm of Hg) of the solution is (take Kb
–1
9. The freezing point of the solution M is = 0.76 K kg mol ). (2012)

(a) 268.7 K (b) 268.5 K (a) 724 (b) 740

(c) 234.2 K (d) 150.9 K (c) 736 (d) 718
10. The vapour pressure of the solution M is 15. 29.2% (w/W) HCl stock solution has density of 1.25 g
(a) 39.3 mm Hg mL–1. The molecular weight of HCl is 36.5g mol–1. The
volume (mL) of stock solution required to prepare a
(b) 36.0 mm Hg
200 mL solution 0.4 M HCl is (2012)
(c) 29.5 mm Hg
16. Benzene and naphthalene form an ideal solution at room
(d) 28.8 mm Hg
temperature. For this process, the true statements is (are)
11. Water is added to the solution M such that the mole fraction
(MCQ)(2013)
of water in the solution becomes 0.9. The boiling point of
this solution is (a) ΔG is positive
(a) 380.4 K (b) ΔSsystem is positive
(b) 376.2 K
(c) 375.5 K (c) ΔSsurroundings =0

(d) 354.7 K (d) ΔH=0

12. The Henry’s law constant for the solubility of N2 gas in 17. Liquids A and B form ideal solution over the entire
5
water at 298 K is 1.0 × 10 atm. The mole fraction of N2 in range of composition. At temperature T, equimolar
air is 0.8. The number of moles of N2 from air dissolved in binary solution of liquids A and B has vapour pressure
10 moles of water of 298 K and 5 atm pressure is 45 Torr. At the same temperature, a new solution of A
(2009) and B having mole fractions xA and xB, respectively,
–4 has vapour pressure of 22.5 Torr. The value of xA/xB in
(a) 4.0 × 10
the new solution is ..............
–5
(b) 4.0 × 10
(given that the vapour pressure of pure liquid A is 20
–4
(c) 5.0 × 10 Torr temperature T)
–6
(d) 4.0 × 10 18. Mixture(s) showing positive deviation from Raoult’s law
at 35ºC is (are) (MCQ)(2016)
13. The freezing point (inº C) of solution containing 0.1g of
K3[Fe(CN)6] (mol. wt. 329) in 100g of water (Kf = 1.86 K (a) carbon tetrachloride + methanol
–1 (b) carbon disulphide + acetone
kg mol ) is (2011)
–2 –2 (c) benzene + toluene
(a) – 2.3 × 10 (b) – 5.7 × 10
–3 –2 (d) phenol + aniline
(c) – 5.7 × 10 (d) – 1.2 × 10
SOLUTIONS 57
19. Pure water freezes at 273 K and 1 bar. The addition of 34.5 solution is 1.2 g/cm3, the molarity of urea solution is_____.
g of ethanol to 500 g of water changes the freezing point (Given data: Molar masses of urea and water are
of the solution. Use the freezing point depression constant 60 g mol–1 and 18 g mol–1, respectively) (2019/Shift-2)
of water as 2 K kg mol-1. The figures shown below
represent plots of vapour pressure (V.P.) versus 22. 5.00 mL of 0.10 M oxalic acid solution taken in a conical
temperature (T). [molecular weight of ethanol is 46 g mol-1] flask is titrated NaOH from a burette using phenolphthalein
indicator. The volume of NaOH required for the appearance
Among the following, the option representing change of permanent faint pink color is tabulated below for five
the freezing point is (2017) experiments. What is the concentration, in molarity, of
the NaOH solution? (2020/Shift-1)
Exp. No. Vol. of NaOH (mL)
1 12.5
(a) 2 10.5
3 9.0
4 9.0
5 9.0
23. Liquids A and B form ideal solution for all compositions
of A and B at 25ºC. Two such solutions with 0.25 and 0.50
(b) mole fractions of A have the total vapor pressures of 0.3
and 0.4 bar, respectively. What is the vapor pressure of
pure liquid B in bar? (2020/Shift-2)
24. The boiling point of water in a 0.1 molal silver nitrate
solution (solution A) is xC. To this solution A. an equal
volume of 0.1 molal aqueous barium chloride solution is
added to make a new solution B. The differnece in the
(c) boiling point of water in the two solutions A and B is
y 102 C. (Assume, Densities of the solutions A and B
are the same as that of water and the soluble salts
dissociate completely. Use: molal elevation constant
(Ebullioscopic constant). kb  0.5 K kg mol 1 ; Boiling
point of pure water as 100C ).
(d) The value of X is______. (2021)
25. The boiling point of water in a 0.1 molal silver nitrate
solution (solution A) is xC. To this solution A. an equal
20. On dissolving 0.5 g of a non-volatile non-ionic solute to volume of 0.1 molal aqueous barium chloride solution is
39 g of benzene, its vapor pressure decreases from 650 added to make a new solution B. The differnece in the
mm Hg to 640 mm Hg. The depression of freezing point of boiling point of water in the two solutions A and B is
benzene (in K) upon addition of the solute is ______
y 102 C. (Assume, Densities of the solutions A and B
(Given data: Molar mass and the molal freezing point
depression constant of benzene are 78 g mol–1 and 5.12 are the same as that of water and the soluble salts
K kg mol–1, respectively) (2019/Shift-1) dissociate completely. Use: molal elevation constant

21. The Mole fraction of urea in an aqueous urea solution (Ebullioscopic constant). kb  0.5 K kg mol 1 ; Boiling
containing 900 g of water is 0.05. If the density of the point of pure water as 100C. )
The value of [y] is______. (2021)
SOLUTIONS 58

Note:

Find Answer Key and Detailed Solutions at the end of this book

SOLUTIONS

Please share your valuable feedback by

scanning the QR code.
SOLID STATE
 Chapter 02 60

SOLID STATE

1. INTRODUCTION 2. CLASSIFICATION OF SOLIDS

Solid state is a state of matter besides liquid and gaseous state. Solids are broadly classified on the basis of following
In case of solids the inter molecular forces are very strong and parameters.
empty spaces between the atoms/ions/molecules is very less.  based on various properties
That is why they have a fixed shape and volume.
 based on bonding present in building blocks.
1.1 Characteristics properties of solids
2.1 On the basis of various properties
Solids are characterised by the following properties
Based on their various properties solids can be classified as
 High density
 Crystalline solids
 Low compressibility
 Amorphous solids.
 Rigidity
Crystalline solids have a regular structure over the entire volume
 Definite shape and volume. and sharp properties whereas amorphous solids have irregular
structure over long distances and properties are not that sharp.
Various differences are listed in table below

Property Crystalline solids Amorphous solids

Shape They have long range order They have short range order.
Melting point They have definite melting point They do not have definite melting point.
Heat of fusion They have a definite heat of fusion They do not have definite heat of fusion
Compressibility They are rigid and incompressible They may be compressed to some extent
Cleavage When cut with a sharp edged tool, they when cut with a sharp edged tool, they cut into
Property Split into two pieces and the newly two pieces with irregular surfaces
generated surfaces are plain and smooth
Isotropy and Anisotropic in nature. physical properties Isotropic in nature. Value of any physical
Anisotropy show different values when measured property would be same along any direction
along different directions in the same
crystals
Volume change There is a sudden change in There is no sudden change in volume on
volume when they melt. melting.
Symmetry They possess symmetry They do not possess any symmetry.
Interfacial angles They possess interfacial angles. They do not possess interfacial angles.

SCAN CODE
SOLID STATE
SOLID STATE
61
2.2 Based on bonding
There are various type of solids based on type of bonding present in their building blocks. Various types of solids along
with their properties are given in the table below. Molecular solid can be classified into three parts.

Different properties of four types of solids

Types of Solid Constituent Nature of Examples Physical Electrical Melting

particls Bonding nature conductivity point
(1) Molecular Molecules
Solids

(i) Non polar Dispersion or Ar, CCl4, H2, Soft Insulator Very low
London forces I2, CO2

(ii) Polar Dipole-dipole HCl, SO2 Soft Insulator Low

Interactions

(iii) Hydrogen Hydrogen H2O (ice) Hard Insulator Low

bonded bonding

(2) Ionic solids Ions Coulombic or NaCl, MgO, Hard but brittle Insulators in High
electrostatic ZnS, CaF2 solid state but
conductors in
molten state
and in aqueous
solutions

(3) Metallic Positive ions Metallic Fe, Cu, Hard but Conductors in Fairly high
solids in a sea of bonding Ag, Mg malleable solid state as
delocalised and ductile well as in
electrons molten state

(4) Covalent or Atoms Covalent SiO2 (quartz) Hard Insulators Very high
network bonding SiC, C
solids (diamond)
AlN,
C(graphite) Soft Conductor
(exception)

SCAN CODE
SOLID STATE
SOLID STATE 62
3. STRUCTURE OF CRYSTALLINE SOLIDS

3.1 Crystal lattice and Unit Cell

The regular array of the building blocks (atoms/ions/molecules)

inside the crystalline solid is called “Crystal Lattice”.

The smallest part or crystal lattice which can be repeated in all

directions to generate entire crystal lattice is called “Unit Cell”.

In unit cell the atoms of ions or molecules are represented by

small spheres. Various lattices are formed by variation in following
parameters:
3.2 Primitive Unit Cells and Bravais Lattices
The edge length along 3 axes - a, b, c
In all, there are seven types of unit cells and there can be some
 The interfacial angles - ,  , . sub types of unit cells. These seven unit cells are called Primitive
Unit Cells . Which are listed in table below.
 Location of atom/ions w.r.t each other in crystal lattice.

Crystal System Possible Unit cell Axial distances Axial angles Examples

Cubic 3 abc       90 Copper, Zinc blende, KCl

Tetragonal 2 abc       90 Sn (White tin), SnO2, TiO2

Orthorhombic 4 a bc       90 Rhombic sulphur, KNO3

Monoclinic 2 a  b  c     90;   90 Monoclinic sulphur, PbCrO2

Hexagonal 1 abc     90;   120 Graphite, ZnO

Rhombohedral 1 abc       90 CaCO3(Calcite),HgS

(Cinnabar)

Triclinic 1 abc       90 K2Cr2O7, CuSO4.5H2O

SCAN CODE
SOLID STATE
SOLID STATE
63
Bravais Lattice

Crystal System Space lattice Examples

Cubic Simple : Lattice Body Centered : Face Centered : Lattice Pb, Hg, Ag,Au,

a  b  c Here, a, b points at the eight Lattice points at the points at the eight corners Cu, ZnS, diamond,

and c are parameters corners of the eight corners and and at the six face centres. KCl, NaCl, Cu2O,

(dimensions of a unit unit cells. at the body centre. CaF2 and alums. etc.

cell along three

axes)] size of

crystals depend

on parameters.

      90, 
and  are

three angles
between the
axes.
Tetragonal Simple : Lattice Body Centered : SnO2, TiO2, ZnO2,

a  b  c. points at the eight Lattice points at the eight corners and at the NiSO4, ZrSiO4,PbWO4,

      90 corners of the unit body centre. white Sn etc.

cells.

Orthorhombic Simple : Lattice End Centered : Body Centered: Face Centered : KNO3, K2SO4,
(Rhombic) points at the eight Also called side Lattice Lattic points at PbCO3, BaSO4
a  b  c. corners of the centered or base Points at the the eight corners Rhombic sulplur.
      90 unit cells. centered. Lattice eight corners and at the six MgSO4.7H2O etc.
points at the eight and at the face centres.
corners and at two body centre.
face centres opposite
to each other.

SCAN CODE
SOLID STATE
SOLID STATE 64
Rhombohedral Simple : Lattice points at the eight NaNO3, CaSO4

or Trigonal corners of the unit cells. calcite, quartz

a  b  c, As, Sb, Bi etc.

      90

Hexagonal Simple : Lattice points at the twelve ZnO, PbS, CdS, HgS,

a  b  c, corners of the unit cell graphite, ice,

    90  120 Mg, Zn, Cd. etc.

Monoclinic Simple : Lattice points at the End Centered : Lattice points at Na2SO4. 10H2O,

a  b  c, eight corners of the unit cells. the eight corners and at two face Na2B4O7.10H2O,

    90,  90 centres opposite to each other. CaSO4.2H2O, mono

clinic sulphur etc.

Triclinic Simple : Lattice points at the eight corners of the CuSO4.5H2O, K2Cr2O7, H3BO3

a  b  c, unit cells.

      90

We will focus majorly on cubic unit cells and their arrangements.

SCAN CODE
SOLID STATE
SOLID STATE
65
3.3 Cubit Unit Cells 3.3.1 Types of cubic Unit Cells

This is the most common unit cell. In a cubic unit cell there are
following locations for the atoms or spheres

* Corners

* Body Centre

* Face Centres
These unit cells differ from each other in following factors.
Following are the contributions of a sphere kept at various * Location of spheres inside the unit cell.
locations. * Rank of the unit cell (effective number of spheres inside a unit
Location Contribution cell) (Z)
* Relation between edge length and radius of one sphere.
Corners 1/8
* Packing fraction (fraction of volume occupied by spheres in a
Body Centre 1 unit cell)
The following parameters for all the 3 unit cells are listed is the
Face Centre 1/2
table below:

Type of No. of atoms at different Structure Rank Packing Relation between

Cublic locations (lattice points) (Z) atomic and radius
Crystal edge length (a)
Corners Body Centre Face Centre

Simple Cubic 8    1 52% r  a/2

3a
Body Centred 8 1   2 68% r
4

2a
Face Centred 8  6 4 74% r
4

SCAN CODE
SOLID STATE
SOLID STATE 66
3.4 Density of cubic crystals b. On other hand if spheres of second layer are placed in
Density of cubic crystal is given by the following formula depressions of first layer we get BCC unit cell and ABAB ….
Type of packing.
M Z
Density   a 3  N Arrangements based on hexagonal foundation layer are as follows
A
If we put 2nd layer in depressions of first hexagonal layer A two
where, Z  rank of unit cell types of voids are created. X type of voids are those which are
hollow and through voids of layer A and layer B. while Y type of
M  Molar mass of solid
voids are those voids of layer B which are exactly above spheres
a  Edge length of unit cell of layer A. If we place the spheres of 2nd layer on Y voids then we
are repeating layer 1 and ABABAB…. Type packing is obtained.
NA  Avogadro Number.
In this arrangement hexagonal unit cell is obtained and packing
3.5 Close packing in Solids : Origin of unit cells is called Hexagonal Close Packing (HCP). The efficiency of this
packing is 74%.
Suppose we have spheres of equal size and we have to arrange If the 3rd layer is placed on X-type of voids then a new layer C is
them in a single layer with the condition that spheres should obtained and then the arrangement will be repeated. We will obtain
come in close contact with each other. Two types of layers are ABCABCABC….. type of packing. The unit cell for this
possible: arrangement is FCC and the packing efficiency is 74%.
1. Square Packing :
In square packing spheres are placed in such a way that the rows
have a horizontal as well as vertical arrangements. In this case
Co-ordination Number is 4.

2. Hexagonal Packing :
Hexagonal packing is more efficient. Its Co-ordination Number is
6 and voids in the packing are smaller than square packing.
Packing of second layer (b) on first layer (a)

If we place another layer on square packing then there are

following possibilities:
a. A similar layer placed just above foundation layer that is the
spheres of the second layer coming just above the spheres of
the first layer and layers get repeated. In first layer is termed A
the packing in this case is AA… type and the unit cell is
simple cubic.
ABABA..... of hcp arrangement of spheres. Metals like
magnesium, zinc, etc. adopt this type of arrangement

SCAN CODE
SOLID STATE
SOLID STATE
67
4.3.2 Tetrahedral Void

It is formed by contact of 4 spheres and is positioned at the

centre of tetrahedron formed by contact of 4 spheres.

Figure Key Points

r
* Radius Ratio  0.225
R
* No. of voids in FCC crystal  8
a 3
* Position : at a distance
4
from every corner.
* Co-ordination no.  4

4.3.3 Octahedral Void

Figure Key Points

ABCABCA ..... of ccp arrangment of spheres r

* Radius Ratio  0.414
R
4. VOIDS
* No. of voids in FCC
4.1 Definition crystal  4
The empty spaces inside a spheres are called “voids”. The size * Position : Body centre,
and shape of voids depends upon the type of unit cell and Edge Centres.
packing. * Rank  4
* Co-ordination no.  4
4.2 Radius Ratio
The size of void is expressed in terms of radius ratio of a sphere 4.3.4 Cubic Void
that can be exactly fit in the void to the radius of surrounding This void is formed by close contact of 8 spheres
spheres. This expressed as:
r Key Points
Radius ratio =
R r
* Radius Ratio  0.732
R
4.3 Types of voids
* No. of voids in cubic crystal  1
4.3.1 Trigonal void
* Position : at body centre
It is a void formed of equal radii and touching each other as
* Co-ordination number  8
shown in figure.
* Rank  1
Figure Key Points
It is clear from above details that
* Radius Ratio Trigonal < Tetrahedral < Octahedral < Cubic
r void void void void
 0.155
R
* Smallest void
* Co-ordination no.  3

SCAN CODE
SOLID STATE
SOLID STATE 68
5. CLASSIFICATION OF IONIC STRUCTURES 5.2 ZnS type Structure

Ionic compounds are formed by the simultaneous arrangement Figure Key Points
of cations and anions in lattice/unit cell. The larger of two species * S2  ions occupy main positions and
occupies major positions in a unit cell and the smaller ones occupy
Zn 2 ions are present in alternate
voids according to their size, which is decided on the basis of
tetrahe dral voids in FCC crystal.
radius ration (r/r). The various ratios are listed below.
* Effective formula  Zn4S4
Limiting C.N. Shape Example * Co-ordination No. of Zn2+  4
Radius Ratios, * Co-ordination No. of S2  4
x  r/r
a 3
* rZn  rS 
2 2
x < 0.155 2 Linear BeF2 4
0.155  x  0.225 3 Plane Triagonal AlCl3
0.225  x  0.414 4 Tetrahedral ZnS
0.414  x  0.732 6 Octahedral NaCl 5.3 Fluorite Type Structure
0.732  x  0.999 8 Cubic CsCl
Figure Key Points
* Ca2+ ions occupy main positions
Based on these ratio ranges, ionic crystal are classified into 5
and F ions occupy tetrahedral
categories which are as follows
voids in FCC crystal.
* Effective formula  Ca4F8
5.1 NaCl Type Structure
* Co-ordination No. of Ca2+  8
* Co-ordination No. of F  4
Figure Key Points
a 3
* Cl occupy corners and face * rCa  rF  4
2 –

centres and Na occupy

octahedral voids in FCC crystal.
5.4 Anti Fluorite Structure
* Effective formula  Na4Cl4
Figure Key Points
* Co-ordination No. of Na  6 * Common in alkali oxides like
Na2O, Li2O etc.
* Co-ordination No. of Cl  6
* O2 ions occupy FCC, Li ions
* Distance b/w nearest
occupy the tetrahedral voids
 a * C.N. of Li  4
neighbours  rNa   rCl  
 2 * C.N. of O2  8
a 3
* rLi  rO 
 2
4

SCAN CODE
SOLID STATE
SOLID STATE
69

5.5 CsCl Type Structure 6.4 Stoichiometric Defects

Figure Key Points These defects do not disturb stoichiometry of solid substance.
* Cl ions simple cubic Locations

6.4.1 Schottky defects
(corners) and Cs ions occupy
body centre in BCC lattice. It is a vacancy defect in ionic solids. No of missing cations and
* Effective formula  CsCl anions is equal so electrical neutrality is maintained. This defect
* Co-ordination No. of Cs  8 decreases the density of the substance. The defect is shown by
* Co-ordination No. of Cl  8 ionic substances in which cation and anion are of almost similar
sizes. Eq. KCl, NaCl, AgBr etc.
a 3
* rCs  rCl 
  .
2

6. IMPERFECTIONS IN SOLIDS

Sometimes some defects or imperfections occur in crystal

structure. Schottky defect
6.1 Classification of defects
6.4.2 Frenkel defect

In ionic solids the smaller ion is dislocated from its normal position
to an interstitial site. It creates a vacancy defect at its original site
and interstitial defect at new location. It is also called as
dislocation defect. It does not change the density of solid.

This type of defect is shown by ionic substances in which there

is a large difference in size of ions. Eq ZnS, AgCl, AgBr etc.

6.2 Vacancies

These are defects that occur when positions that should

contain atoms or ions are vacant.

6.3 Interstitial sites

These are sites located between regular positions sometimes

atoms or ions may occupy these positions.
Frenkel defect

NOTE
AgBr shows both Schottky and Frenkel defects.

SCAN CODE
SOLID STATE
SOLID STATE 70
6.5 Non Stoichiometric Defects 6.5.2 Metal Deficiency Defect

The compounds having these defects contain combining This defect occurs when metal shows variable valency. eq. FeO
elements in a ratio different from required by their stoichiometric is mostly found is varying compositions between Fe 0.93O to
Fe0.96O. in crystals of FeO some Fe cations are missing and the
formulae.
loss of positive charge is made up by the presence of required
6.5.1 Metal Excess Defect number of Fe ions.

Due to anionic vacancies : The anion may be missing from its 7. ELECTRICAL & MAGNETIC PROPERTIES
lattice site leaving an e- behind so that charge remains balanced.
The site containing electron is called F centre. They impart colour 7.1 Electrical Properties of Solids
to the crystal, F stands for Farbenzenter meaning colour. Solids can be classified into three types on the basis of their
conductivities.
This defect is similar to schottky defect and is found is crystals
having schottky defect eq. NaCl, KCl etc. Classification of Solids on the Basis of Electrical Conductivity

Type of solid Conductivity Reason of Examples

(ohm-1 m-1) conductivity
Conductors 104 to 107 Motion of Metals like
(very high) electrons Ag, Al, etc.
Insulators 10-20 to 10-10 Do not permit Wood,
(very low) electricity to Rubber,
pass Bakelite
Semiconductors 10-6 to 104 Motion of Si, Ge, etc.
(moderate) interstitial
electrons or
holes or both
An F-Centre in a crystal
7.2 Band theory
Due to the presence of extra cations in the interstitial sites.
Band theory of metals is based on valence band and conduction
An extra cation may be present in interstitial site and an electron
band. It is also known as band theory of solids or zone theory of
is present in another interstitial site so that electrical neutrality is
solids. It defines conductors, semiconductors and insulators very
maintained. This is similar to Frenkel defect and if found in crystal
clearly and distinctly.
having Frenkel defect.
Valence band :
The energy band that consists of valence electrons is known as
the valence band.
Conduction band :
The energy band that consists of free electrons is known as the
conduction band.
Forbidden band :
The energy gap between the valence band and the conduction
band is known as the forbidden band which is also known as the
forbidden gap.
Metal excess defect caused by extra
cation in the interstitial site

SCAN CODE
SOLID STATE
SOLID STATE
71

Creation of n-type and p-type semiconductors

by doping groups 13 and 15 elements

7.3 Magnetic Properties of Solids

Every substance has some magnetic properties associated with
Distinction among conductors, insulators and semiconductors it. The origin of these properties lies in the electrons. Each elec-
In each case, an unshaded area represents a conduction band tron in an atom behaves like a tiny magnet. Its magnetic moment
originates from two types of motions (i) its orbital motion around
Semiconductor :
the nucleus and (ii) its spin around its own axis. Electron being a
Electronic conductors having electrical conductivity in the charged particle and undergoing these motions can be consid-
range of 104  106  1m 1 are known as semiconductors, ered as a small loop of current which possesses a magnetic mo-
e.g. Si, Ge, Sn (grey), SiC and GaAs. ment. Thus, each electron has a permanent spin and an orbital
magnetic moment is associated with it. Magnitude of this mag-
netic moment is very small and is measured in the unit called Bohr
Doping : magneton, µB. It is equal to 9.27 × 10–24 A m2.
In semiconductor production, doping is the intentional intro-
duction of impurities into an intrinsic semiconductor for the
purpose of modulating its electrical, optical, and structural
properties.

Intrinsic Semiconductors :
Pure substances that are semiconductors are known as
intrinsic (undoped) semiconductors, e.g. Si, Ge.
Demonstration of the magnetic moment associated with (a) an
Extrinsic Semiconductors : orbiting electron and (b) a spinning electron
Their conductivity is due to the presence of impurities.
They are formed by doping. It is defined as addition of Solids can be divided into different classes depending
impurities to a semiconductor to increase the conductivity. on their response to magnetic field.
Doping of Si or Ge is carried out with P, As, Sb, B, A1 or Ga. Paramagnetic Substances :
(i) n-type semiconductors : These are attracted by the magnetic field and have unpaired elec-
Silicon or germanium doped with 15 group elements like phospho- trons.
rus is called n-type semiconductor. These lose magnetism in the absence of magnetic field,
The conductivity is due to the presence of negative e.g. O2 , Cu 2 , Fe3 ,etc.
charge (electrons).
Diamagnetic Substances :
(ii) p-type semiconductors :
These are weakly repelled by the magnetic field and do not have
Silicon or germanium doped with 13 group element like any unpaired electron, e.g. TiO2, V2O5,
gallium is called p-type semiconductor. The conductivity is due C6H6, NaCl, etc.
to the presence of positive holes. Some typical 13-15 compounds
are InSb, AlP and GaAs and some typical 12-16 compounds are
ZnS, CdS, CdSe and HgTe. These exhibit electrical and optical
properties of great use in electronic industry.

SCAN CODE
SOLID STATE
SOLID STATE 72
Ferromagnetic Substances : Ferrimagnetic Substances :
These are attracted by the magnetic field and show These substances have a net dipole moment due to unequal par-
permanent magnetism even in the absence of magnetic field, e.g. allel and anti-parallel alignment of magnetic moments, e.g. Fe3O4,
Fe, Co, CrO2 and Ni. ferrites  M Fe 2 O 4  , where M = Mg, Cu, Zn etc.
2

Schematic alignment of magnetic moments in Ferromagnetic

Substances Schematic alignment of magnetic moments in Ferrimagnetic
Anti-ferromagnetic Substances : Substances
These substances have net magnetic moment zero due to com-
pensatory alignment of magnetic moments, e.g.
MnO, MnO2, FeO, NiO, Cr2O3 etc.

Schematic alignment of magnetic moments in

Anti-ferromagnetic Substances

SCAN CODE
SOLID STATE
SOLID STATE
73

SUMMARY

SCAN CODE
SOLID STATE
SOLID STATE
74

SOLVED EXAMPLES

Example - 1 (a) Metallic solids (e.g., zinc, chromium, etc.)

Why are solids rigid ? (b) Ionic solids (e.g., sodium chloride, potassium bromide)
Sol. Solids are rigid because the intermolecular forces of (c) Covalent solids (e.g., diamond, graphite)
attraction that are present in solids are very strong. The (d) Molecular solids (e.g., iodine, naphthalene)
constituent particles of solids cannot move from their
Example - 5
positions, that is, they have fixed positions.However, they
can oscillate about their mean positions.
What difference in behavior between the glass and
Example - 2 sodium chloride would you expect to observe if you break
Why does the window glass of the old buildings look off a piece of either cube ?
milky?
Sol. If we break or cut a piece of cube of sodium chloride, then
Sol. Due to continuous heating in the day and cooling at night, we will observe that the surfaces on the two portions of
that is, annealing over a long period, glass acquires some the cube after breaking will be smooth but in case of glass
crystalline characteristics. Glass is generally amorphous
crystals the two surfaces of the cube after breaking will be
by nature, but due to annealing it becomes crystalline in
irregular. This is because of the cleavage property of
nature. Hence, window glass of the old buildings looks
crystalline solids according to which if we break or cut a
milky.
crystalline solid then we get two smooth surfaces, but
Example - 3
amorphous solids do not show cleavage property.
Why does urea have a sharp metling point but glass Therefore in case of amorphous solids after cutting we get
does not ? two irregular surfaces.

Sol. Urea is a crystalline solid, whereas glass is an amorphous Example - 6

solid. Crystalline solids have sharp melting points, whereas
amorphous solids do not possess sharp melting points. Identify the forces that must be overcome to cause melting
Example - 4 in the following solids. Rank the compounds in the order
of expected melting points (lowest one first) :
What are crystalline solids ? State the categories of
(a) Diamond ; (b) CF4 ; (c) CrF2 ; (d) SCl2.
crystalline solids with examples.
Sol. (a) Diamond Network (solid) covalent bonds
Sol. Crystalline solids are solids with highly ordered
arrangement of constituent particles that is repeated many (b) CF4 London dispersion forces
times throughout the structure. The pattern is so ordered (c) CrF2 Electrostatic forces
and regular that arrangement of constituent particles at
(d) SCl2 London forces and dipole-dipole forces
any site can be predicted, if arrangement at any one site is
known. They are characterized by rigid structure, high and The order is : CF4 < SCl2 < CrF2 < diamond.
sharp melting points.
SOLID STATE
75
Example - 7 (b) A face-centered unit cell has one constituent particle
present at the center of each face in addition to the
Compare and contrast the bonding in molecular solids particles present at the corners as shown in fig.
and network covalent solids. Which would you expect An end-centered unit cell has one constituent
to have a higher melting point, molecular solids or particle each at the center of any two opposite faces
network covalent solids ? in addition to the particles present at the corners as
shown in fig.
Sol. In molecular solids, the constituent particles are molecules.
The forces operating between them are weak dispersion
forces or dipole-dipole forces of attraction or hydrogen
bonding depending on the type of molecular solid. In
covalent or network solids, the constituent particles are
non-metal atoms linked to adjacent atoms by covalent
bonds throughout the solid.
Covalent or network solids have a higher melting point
than molecular solids.
Example - 8

MgO has the structure of NaCl, and TiCl has the structure (a) (b)
of CsCl. What are the coordination numbers of the ions Example - 12
in MgO and TiCl ?

Sol. The coordination number of ions in MgO is 6 and What relationship is there between a crystal lattice and a
coordination number of ions in TiCl is 8. unit cell ?

Example - 9 Sol. Crystal lattice : A regular arrangement of the constituent

particles of a crystal in a three dimensional space is called
What type of solids are electrical conductors, malleable crystal lattice or space lattice.
and ductile.
Unit cell : The smallest three-dimensional portion of a
Sol. Metallic solids are electrical conductors, malleable and complete space lattice, which when repeated over and
ductile. again in different directions produces the complete space
lattice.
Example - 10
Example - 13
Give the significance of a “lattice point”.
A solid is made up of two elements P and Q. Atoms Q
Sol. The significance of a lattice point is that each lattice point
are in ccp arrangement while atoms P occupy all the
represents one constituent particle of the solid which may
tetrah edra l sites. Wh at is t he form ula of t he
be an atom, a molecule (group of atoms), or an ion.
compound ?
Example - 11
Sol. Suppose number of atoms of element Q = N. So, number of
Distinguish between tetrahedral sites = 2N. Therefore, the number of atoms of
element P = 2N. The ratio P : Q = 2N:N = 2:1. Hence, the
(a) Hexagonal and monoclinic unit cells.
formula of the compound is P2Q.
(b) Face-centered and end-centered unit cells.

Sol. (a) For a hexagonal unit cell, a = b  c and  =  = 90º, = 120º
For a monoclinic unit cell, a  b  c and  =  = 90º,  90º
SOLID STATE
76
Example - 14 Example - 18

Name the parameters that characterize a unit cell. A compound with fcc crystal structure has a density of
2.163 × 103 kg m–3. Calculate the edge length of its unit
Sol. The parameters that characterize a unit cell are as follows: cell. The molar mass of the compound is 58.2 g mol–1.
(a) Its dimensions along the three edges a, b and c. These
edges may or may not be equal. Sol. For an element, the density of a crystal is given by
(b) The angles between the edges. These are represented
Z M
by  (between edges b and c),  (between edges a and  ... 1
a3  NA
c) and  (between edges a and b).
Example - 15 where Z is the number of particles present per unit cell; M
is the atomic mass of the element ; a is the edge length of
A cubic solid is made up of two elements X and Y. Atoms Y the unit cell; NA is the Avogadro constant ;  is density of
are present at the corners of the cube and atoms X at the
the crystal given as 2.163 × 103 kg m–3. Since density is
body center. What is the formula of the compound? What
are the coordination numbers of X and Y ? usually expressed in g cm–3, so

Sol. Number of atoms of X and number atoms of Y = 1. The 2.163 103 103 2.163 106
  = 2.163 g cm–3
formula of the compound is XY. The coordination number (1 102 )3 106
of the compound will be 8 because one X atom is
For fcc crystal structure, Z = 4 and we know that
surrounded by eight Y atoms at the corner of the cube.
NA = 6.02 × 1023 mol–1 M = 58.2 g mol–1. Rearranging Eq. (1)
Example - 16 in terms of a, we get

Gold (atomic radius = 0.144 nm) crystallizes in a face- Z M 4  58.2 g mol 1

a3  
centered unit cell. What is the length of a side of the cell?   N A 2.163  6.02 1023 mol 1g cm 3

Sol. For a face-centerd unit cell, a = 2 2r It is given that the 232.8 g mol 1
atomic radius, r = 0.144 nm. So,   17.880 10 23 cm 3
13.02 1023 g cm 3mol 1
a  2 2  0.144 = 0.407 nm = 178.8 × 10–24 cm3
Hence, length of a side of the cell = 0.407 nm. So, the edge length of the unit cell is
Example - 17 a = (178.8)1/3 × 10–8 = 5.634 × 10–8 cm or 563.4 pm.
Example - 19
The atomic radius of nickel is 124 pm. Nickel crystallizes
in face-centered cubic lattice. What is the length of the
edge of unit cell expressed in pm and angstroms ? The figures given below show the location of atoms in
three crystallographic planes in a fcc lattice. Draw the
Sol. In a fcc, edge length = a and the radius of each atom be r. In unit cell for the corresponding structure and identify these
this structure, atoms touch each other along the face- planes in your diagrams.
diagonal, therefore

Face diagonal = 2a  4r

4r
or a  2 2  124 pm = 350.7 pm
2 Sol. Face centred cube, face diagonal plane, diagonal plane.
thus, the unit cell edge length is 350.7 pm.
SOLID STATE
77
Example - 20 = 40 × 40 = 1600 mm2 = 16 cm2 ( 40 mm = 4 cm)
= 4 × 4 cm2
How many copper atoms are there within the face-
centered cubic unit cell of copper ?

Sol. In the face-centered cubic unit cell, there are eight atoms at
the corners and six atoms on the faces. Therefore, the
contribution of atom at the corners = 1/8 × 8 = 1, and
contribution of atoms on the faces = 1/2 × 6 = 3. Thus the
number of copper atoms present is four per unit cell.
Example - 21
A compound formed by elements A and B has a cubic
structure in which A atoms are at the corners of the cube
and B atoms are at the face centers. Derive the formula of Maximum no. of spheres = 14 (full)
the compound. + 8 (half) = 18
Sol. As a atoms are present at the 8 corners of the cube, therefore
18
number of atoms of A in the unit cell = 1/8 × 8 = 1. As B Molecule Per unit area  =1.125
atoms are present at the face centers of the cube, therefore 16
number of atoms of B in the unit cell = 1/2 × 6 = 3. Therefore, Example - 24
ratio of atoms A:B = 1:3. Hence, the formula of compound
is AB3. A solid substance AB has a rock salt geometry. What are
Example - 22 the coordination numbers of A and B ? How many atoms
of A and B are present in the unit cell ?
Explain how much portion of an atom is located at Sol. The coordination number of A and B is 6. Four atoms each
(a) corner and (b) body center of a cubic unit cell is part of A and B are present in the unit cell.
of its neighboring unit cell.
Example - 25
Sol. (a) An atom located at the corner of a cubic unit cell is
shared by eight adjacent unit cells. Therefore, 1/8th The unit cell of a substance has cations A+ at the corners
portion of the atoms belongs to one unit cell. of the unit cell and the anions B– in the center. What is
the simplest formula of the substance ?
(b) An atom located at the body center of a cubic unit cell
is not shared by any other unit cell. Hence, it belongs
Sol. Number of cations (A+) per unit cell = 8 × 1/8 = 1
fully to the unit cell.
Number of anions (B–) per unit cell = 1
Example - 23
Hence, the ratio of A+ : B– is 1 : 1 and the formula of the
compound is AB.
You are given marbles of diameter 10 mm. They are to be
placed such that their centers are lying in a square bound Example - 26
by four lines and each at length 40 mm. What will be the
arrangments of marbles in plane so that maximum number Which of the following lattices has the highest packing
of marbles can be placed inside the area ? Sketch the efficiency : (a) Primitive cubic (b) body-centered cubic
diagram and find the value of the number of molecules and (c) hexagonal close-packed lattice ?
per unit area.
Sol. Hexagonal close-packed lattice has the highest packing
efficiency of 74%. The packing efficiencies of primitive
Sol. Maximum number of marble balls or spheres can be
cubic and body-centered cubic lattices are 52.4% and 68%,
accommodated if they are arranged in a hexagonal close respectively.
packing (hcp).
Area of square having 4 lines each of 40 mm is
SOLID STATE
78
Example - 27 Sol. The edge length of unit cell a = 300 pm = 300 × 10–10 cm,
density of element  = 5.2g-cm–3, mass of the element
A compund form is formed by two elements M and N. m = 200 g. Let the molecular mass of the element be M and
The element N forms ccp and atoms of M occupy 1/3rd number of moles be n then we have
of tetrahedral voids. What is the formula of the
compound? m m
n M 
M n
Sol. The ccp lattice is formed by the atoms of the element N.
Here, the number of tetrahedral voids generated is equal to For bcc structure, Z = 2. Now using the relation
twice the number of atoms of the element N. According to
the questions, the atoms of element M occupy 1/3rd of the m
Z 
ZM n Zm
ratio of the number of atoms of M to that of N is   3   n  3
M : N = (2/3) : 1 = 2:3. Thus, the formula of the compound a3  NA a  NA a  NA  
is M2N3.
2  200
 10 3
Example - 28 (300 10 )  6.02 1023  5.2
The required number of atoms will be N = NA × n
The mineral haematite, Fe2O3 consists of a cubic close-
packed array of oxide ions with Fe3+ ions occupying 2  200
= 6.02 × 1023 × 10 3
interstitial positions. Predict whether the iron ions are in (300 10 )  6.02  1023  5.2
the octahedral holes. Radius of Fe3+ = 65 pm and that of
O2– = 145 pm. = 2.85 × 1024
Example - 31

r 65 pm
Sol. The radius ratio is   0.45
r  145 pm A metal with atomic mass 27 has a density of 2.7 g cm–3
and its unit cell has an edge of 4 Å, what is the nature of
This lies in the range 0.414 – 0.732. Hence, Fe3+ ions will be the crystal lattice for the metal ?
in the octahedral holes.
Sol. The density is given by
Example - 29
Z M

Barium crystallizes in a body-centered cubic structure in a3  NA
which the cell-edge length is 0.5025 nm. Calculate the
shortest distance between neighboring barium atoms in Rearranging in terms of Z, and substituting values, we get
the crystal.
  a 3  N A 2.7  (4 108 )3  6.02 1023
Sol. From the geometry of the body-centered cubic structure, Z 
we find the shortest distance between barium atoms will M 27
occur down the body diagonal where = 3.85  4
Diagonal = 3a  4rBa2  which means that the nature of crystal lattice is face-
centered cubic.
3
r   0.5025 107 cm = 2176 × 10–8 cm Example - 32
Ba 2  4
 .
The shortest distance between barium atoms will be 2rBa The density of chromium metal is 7.2 g cm–3. If the unit
–8
Thus, Ba-Ba distance = 4.352 × 10 cm. cell has edge length of 289 pm, determine the type of
unit cell. (Atomic mass of Cr = 52 u;
Example - 30
NA = 6.02 × 1023).
An element occurs in bcc structure with cell edge 300 Sol. Edge length of unit cell a = 289 pm = 289 ×10 –10 cm, molecular
pm. The density of the element is 5.2 g cm–3. How many mass of chromium M = 52 g mol–1, density of chromium
atoms of the element does 200 g of the element contain ?
SOLID STATE
79
metal  = 7.2 g cm–3. Let the number of atoms be Z. The Example - 34
density can be calculated using the relation
Silver crystallizes in a cubic close-packed structure. The
Z M radius of a silver atom is 1.44 Å. Calculate the density of

a 3NA Ag.

Therefore, Sol. The density is calculated as

Z M

3 10 3
a N A 7.2  (289 10 )  6.023 10 23 a3  NA
Z  2
M 52
where for ccp structure, Z = 4 and r = 1.44 Å. The
Since the unit cell has 2 atoms, hence it is body-centered
relationship between radius of an atom with the edge length
cubic (bcc).
a for ccp crystal structure is r = 0.3535a.
Example - 33
1.44
a  4.07Å  4.07 108 cm
An element with molar mass 2.7 × 10–2 kg mol–1 forms a 0.3535
cubic unit cell with edge length 405 pm. If its density is Substituting these values and using M for Ag = 107.87 g
2.7 × 103 kg m–3, what is the nature of the cubic unit
mol–1, we get
cell?
4 107.87
Sol. It is given that density of the element,  = 2.7 × 103 ; molar  = 10.63 g cm–3
(4.07 108 )3  6.02 1023
mass, M = 2.7 × 10–2 kg mol–1 ;
edge length, a = 405 pm = 405 × 10–12 m = 4.05 × 10–10 m. Example - 35
Applying the relation, for density, we get
A metal (atomic mass = 50) has a body-centered cubic
(using NA = 6.023 × 1023 mol–1)
crystal structure. The density of the metal is
Z M 5.96 g cm –3 . Find the volume of the unit cell

a3  NA (NA = 6.023 × 1023 atoms mol–1).

Therefore, Sol. Atomic mass of metal M = 50 g mol–1 ; density of the metal

is  = 5.96 g cm–3. For body-centered cubic crystal, Z =2.
  a3NA
Z Avogadro’s cosntant NA = 6.023 × 1023 atoms mol–1. Let
M
the volume of the crystal be V. Now, using relation for
density
2.7  103 kgm 3  (4.05  10 10 m) 3  6.022  1023 mol 1

2.7 10 2 kg mol 1 Z M ZM 2  50
 V 
V  NA  N A 5.96  6.023  10 23
= 4.004  4
This implies that four atoms of the element are present per
 2.786  10  23 cm 3
unit cell. Hence, the unit cell is face-centered cubic (fcc) or
cubic close-packed (ccp). Hence, volume of the unit cell = 2.786 × 10–23 cm3.
SOLID STATE
80

Example - 36
1/ 3
 4  119 
a   
23 
 a = 6.6×10–8 cm
Iron (II) oxide has a cubic structure and each unit cell  2 . 75  6 .02  10 
has side 5 Å. If the density of the oxide is 4 g cm–3,
In an fcc, the ions/atoms touch each other along the face
calculate the number of Fe2+ and O2– ions present in diagonal.
each unit cell (molar mass of FeO = 72 g mol–1,
NA= 6.02 × 1023 mol–1.) Face diagonal = 2 a = 2 × 6.6 × 10–8 cm = 9.334 × 10–8 cm

The distance between K+ and Br– = 1/2 (face dagonal)

Sol. Edge length of each unit cell of iron (II) oxide is a = 5 Å
= 1/2 × 9.33 × 10–8 cm = 4.667 × 10–8 cm
= 5 × 10–8 cm. The density of iron (II) oxide is  = 4 g cm–3;
the molecular mass of iron (II) oxide is M = 72 g mol–1 ; Example - 38
Avogadro’s constant is NA = 6.02 × 1023 mol–1. Let the
A unit cell of sodium chloride has four formula units. The
number of Fe2+ and O2– ions present in each unit cell be Z.
edge length of the unit cell is 0.564 nm. What is the density
Now using the relation for density we get
of sodium chloride ?

Z M   a3  NA Sol. No. of atoms in fcc unit cell = 4

 Z 
a 3  NA M
Mol. wt. of NaCl = 23 + 35.5 = 58.5
Length of edge of unit cell = 0.564 × 10–9 m
8 3 23
4  (5 10 )  6.02 10
 4 = 0.564 × 10–7 cm
72
Volume of unit cell = (0.564 × 10–7)3
2+ 2–
Hence the number of Fe and O ions present in each
unit cell will be Z = 4. 4  58.5
Density of NaCl = 7 3
(0.564  10 )  6.023 1023
Example - 37
= 2.165 g/cm3
KBr has fcc structure. The density of KBr is 2.75 g cm–3.
Find the distance between K+ and Br–. Example - 39
(Atomic mass of Br = 80.0).
The density of mercury is 13.6g/mL. Calculate
Sol. For KBr which has fcc structure, Z = 4 ; Avogadro’s approximately the diameter of an atom of mercury
constant NA = 6.02 × 1023 mol –1 ; density of KBr is assuming that each atom is occupying a cube of edge
length equal to the diameter of mercury atom.
 = 2.75 g cm–3 ; the moelcular mass of KBr = 119 g mol–1.
Let the distance between K+ and Br– be a. Now using the Sol. d = 13.6 g/mL
relation for density, we get At. mass of Hg = 200 = M
wt. of 1 mole of Hg = 200gm = wt of 6.023 × 1023 atoms
Z M Z M  4 119  No. of atoms present in 1 g of Hg
  a3    
3
a  NA   N A  2.75  6.02 10 
23
6.023 1023
  3.0115  1021
200
Volume of 1 atom of Hg or unit cell
SOLID STATE
81
1 g of Hg Example - 43

No. of atoms  density
What are the two ways by which non-stoichiometric
1 defects due to metal deficiency may occur ?
  2.44  10  23 cm 3
13.6  3.0115  10 21 Sol. Non-stoichiometry implies that either metal or non-metal
Edge length = Diameter of Hg atom atoms are present in excess. When non-metal atoms are in
excess, two types of defects may arise due to metal
Diameter of 1 atom of Hg = (Volume of unit cell)1/3
deficiency. In the first type of defect, a positive ion is absent
= (2.44 × 10–23)1/3 from its lattice site and the charge is balanced by adjacent
d = (24.40 × 10–24)1/3 = 2.91 × 10–8 cm = 2.91 Å metal (positive) ion having higher oxidation state, for
example, FeO, FeS, etc. In the second type of defect, an
Example - 40 extra negative ion is present in an interstitial position and
the charge balance is maintained by the adjacent metal
Explain how vacancies are introduced in an ionic solid atom having higher charge.
when a cation of higher valence is added as an impurity
in it. Example - 44

Sol. When a cation of higher valence is added to an ionic solid Ionic solids, which have anionic vacancies due to metal
as an impurity in it, the cation of higher valence replaces excess defect, develop color. Explain with the help of a
more than one cation of lower valence so as to keep the suitable example.
crystal electrically neutral. As a result, some sites become
vacant. For example, when Sr2+ is added to NaCl, each Sr2+ Sol. The color develops because of the presence of electrons
ion replaces two Na+ ions. However, one Sr2+ ion occupies in the anionic sites. These electrons absorb energy from
the site of one Na+ ion and the other site remains vacant. the visible part of radiation and get excited. For example,
Hence, vacancies are introduced. when crystals of NaCl are heated in an atmosphere of
sodium vapours, the sodium atoms get deposited on the
Example - 41 surface of the crystal and the chloride ions leave their extra
electrons at the lattice site and diffuse to the surface to
Why does Frenkel defect not change the density of AgCl form NaCl with the deposited Na atoms. The electron
crystals ? occupying the anionic lattice site is known as an F-center.
Sol. Frenkel defect does not change the density of AgCl crystals Example - 45
because in the Frenkel defect, the ions are not removed
from the crystal. So there will be no change in the crystal What are the possible type of defects that can occur if a
structure, that is, there is no decrease in the number of
ions. All the ions are inside the crystal, they are only Ca2+ ion replaces a Na+ in a crystal lattice of NaCl ?
dislocated.
Sol. When a Ca2+ ion replaces a Na+ in a crystal lattice of NaCl,
Example - 42 one extra positive charge is introduced. The Na+ vacancy
or Cl– interstitial will be formed to balance the charge.
What type of defect can arise when a solid is heated ? Hence, the possible defects that can occur are Schottky
Which physical property is affected by it and in what defects.
way ?
Example - 46
Sol. When a solid is heated, vacancy defect can arise. A solid
crystal is said to have vacancy defect when some of the Which point defect in its crystal units alters the density
lattice sites are vacant. Vacancy defect leads to a decrease of a solid ?
in the density of the solid.
Sol. Schottky defect decreases the density of the solid.
SOLID STATE
82
Example - 47 Example - 51

What type of stoichiometric defect is shown by What is the origin of the magnetic properties of an atom ?
(a) ZnS and (b) AgBr ?
Sol. The origin of magnetic properties of an atom lies in the
Sol. (a) ZnS shows Frenkel defect. magnetic moment that arises from two types of motion of
(b) AgBr shows Frenkel as well as Schottky defects. the electrons in the atom. An electron spins around its axis
and moves in its orbital around the nucleus. These motions
Example - 48 of the electron (charge particle) can be considered as a
loop of current and impart permanent spin and an orbital
Mention one property which is caused due to the
magnetic moment to it. The magnitude of this magnetic
presence of F-center in a solid. moment is small and measured in the unit called Bohr
magneton.
Sol. One property which is caused due to the presence of F-
center in a solid is appearance of color. Example - 52

Example - 49 A Group 14 element is to be converted into n-type

semiconductor by doping it with a suitable impurity. To
What other element may be added to silicon to make electrons which group should this impurity belong ?
available for conduction of an electric current ?
Sol. An n-type semiconductor conducts electricity because of
Sol. Silicon is used to create most semiconductors commercially. the presence of extra electrons. Therefore, a Group 14
To make electrons available for conduction of an electric element can be converted to n-type semiconductor by
current, we add Group 15 elements (phosphorus, arsenic, doping it with a Group 15 element.
antimony) to silicon which is tetravalent by nature. With Example - 53
the addition of each Group 15 element, an excess electron
is created which results in conduction of the current. Why does germanium act as an n-type semiconductor ?

Example - 50 Sol. Germanium acts as n-type semiconductor when a

pentavalent impurity atom is added to pure germanium
What type of substances would make better permanent crystal. With addition of each impurity atom, one extra
magnets, ferromagnetic or ferrimagnetic. Justify your electron is created in the crystal lattice of germanium and
answer. hence the majority charge carriers are electrons in n-type
semiconductors.
Sol. Ferromangetic substances would make better permanent Example - 54
magnets. In solid state, the metal ions of ferromagnetic
substansces are grouped together into small regions. These Classify each of the following as being either a p-type
regions are called domains and each domain acts as a tiny semiconductor or n-type semiconductor:
(a) Ge doped with In ; (b) Si doped with B.
magnet. In an unmagnified piece of a ferromagnetic
substance, the domains are randomly oriented. As a result, Sol. (a) Ge (a Group 14 element) is doped with In (a Group 13
the magnetic moments of the domain get cancelled. element). We know that germanium is tetravalent, and that it
However, when the substance is placed in a magnetic field, is surounded by four other germanium atoms in close-packed
all the domains get oriented in the direction of the magnetic structure. Now when an indium atom is added, which is
field and a strong magnetic effect is produced. The ordering trivalent, a hole is created due to the absence of an electron in
of the domains persists even after the removal of the lattice site as shown in fig. and the semiconductor generated
magnetic field. Thus, the ferromagnetic substance becomes
a permanent magnet.
SOLID STATE
83
will be a p-type semiconductor. As the radius of the cation C+ (50 pm) is smaller than the
size of the tetrahedral void, it can be placed into the
tetrahedral void (but not exactly fitted into it).
Example - 57

Predict the structure of MgO crystal and coordination

number of its cation in which cation and anion radii are
equal to 65 pm and 140 pm, respectively.

Sol. Radius of the cation is r + = 65 pm and radius of anion is

r– = 140 pm. Therefore, the radius ratio is
(b) When Si (a Group 14 element) is doped with B
(a Group 15 element). We know that silicon is tetravalent by
nature which means each silicon atom is surrounded r 65 pm

  0.464
by four other silicon atoms. When one boron atom (trivalent r 140 pm
in nature) is added to silicon atoms, then one extra hole is
Since the radius ratio (0.464) is in between 0.414 and 0.732,
created in crystal lattice and the semiconductor generated
will be called as p-type semiconductor. Mg 2+ ions occupy octahedral voids. Therefore, the
coordination number of the cation is 6.
Example - 55
Example - 58
Where are in the periodic table the atoms that are most
likely to be involved in the formation of semiconductors AgI crystallizes in cubic close-packed ZnS structure.
located ? What fraction of tetrahedral sites is occupied by Ag+
ions ?
Sol. Semiconductors are typically formed by elements of Group
13–16, for example B, Si, Al, Ge. Sol. In the face-centered unit cell of AgI, there are four I– ions.
Example - 56 As there are four I– ions in the packing, therefore there are
eight tetrahedral voids. Of these, half are occupied by silver
A solid A+B– has NaCl type close-packed structure. If cations.
the anion has a radius of 241.5 pm, what should be the
ideal radius of the cation ? Can a cation C+ having radius Example - 59
of 50 pm be fitted into the tetrahedral hole of the crystal
A+B– ? An element occurs in bcc structure with a cell edge of 288
pm. The density of metal is 7.2 g cm-3 How many atoms
+ – +
Sol. As A B has NaCl structure, A ions will be present in the
does 208 g of the elements contain?
octahedral voids. Ideal radius of the cation will be equal to
the radius of the octahedral void because in that case, it 3

will touch the anions and the arrangement will be close- Sol. Volume of the unit cell   288  10 10 
packed. Hence,
 23.9 1024 cm3
Radius of octahedral void rA  = 0.414 × rB
208
Volume of 208 g of the element   28.88 cm 3
= 0.414 × 241.5 pm 7.2
= 100.0 pm 28.88

Number of unit cells in 28.88cm3 23.9 10 24
Radius of tetrahedral void = 0.225 × rB
= 0.225 × 241.5 pm  12.08  1023 unit cells
= 54.3 pm Each bcc structure contains 2 atoms.
SOLID STATE
84
23
So, Total atoms in 12.08  10 unit cells
 2  12.08  10 23
 24.16  10 23
Example - 60

In a compound nitrogen atoms (N) make cubic close packed

lattice and metal atoms (M) occupy one-third of the
tetrahedral voids present. Determine the formula of the
compound formed by M and N.

Sol. Let the number of N atoms in ccp is x

 Number of tetrahedral voids = 2x

1
 Number of M atoms   2x
3
Number if N atoms 3x 3
 
Number of M atoms 2x 2

So, the formula of the compound is M2N3

SOLID STATE 85

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Classification of Solids Crystal System and Bravais System and Analysis of
1. Amorphous substances show Cubic System
(1) Short and long range order 10. Which type of crystals contains more than one Bravais
(2) Short range order lattice?

(3) Long range order (a) Hexagonal (b) Triclinic

(4) Have no sharp M.P. (c) Rhombohedral (d) Monoclinic

11. The number of spheres contained (i) in one body centred
(a) 1 and 3 are correct (b) 2 and 3 are correct
cubic unit cell and (ii) in one face centred cubic unit cell, is
(c) 3 and 4 are correct (d) 2 and 4 are correct (a) In (i) 2 and in (ii) 4 (b) In (i) 3 and in (ii) 2
2. Amorphous solids are (c) In (i) 4 and in (ii) 2 (d) In (i) 2 and in (ii) 3
(a) Solid substance in real sense 12. The number of atoms or molecules contained in one body
(b) Liquid in real sense centered cubic unit cell is
(c) Super cooled liquid (a) 1 (b) 2
(d) Substance with definite melting point (c) 4 (d) 6
3. Crystalline solids are 13. Number of atoms in the unit cell of Na (bcc type crystal)
(a) Glass (b) Rubber and Mg (fcc type crystal) are, respectively
(c) Plastic (d) Sugar (a) 4, 4 (b) 4, 2
4. A crystalline solid (c) 2, 4 (d) 1, 1
(a) Changes abruptly from solid to liquid when heated 14. An ionic compound has a unit cell consisting of A ions at
(b) Has no definite melting point the corners of a cube and B ions on the centres of the faces
(c) Undergoes deformation of its geometry easily of the cube. The empirical formula for this compounds
would be
(d) Has an irregular 3-dimensional arrangements
(a) A3B (b) AB3
5. Which of the following is a molecular crystal
(a) SiC (b) NaCl (c) A2B (d) AB

(c) Graphite (d) Ice 15. Copper crystallizes in fcc with a unit cell length of 361 pm.
What is the radius of copper atom ?
6. Solid CO2 is an example of
(a) Molecular crystal (b) Ionic crystal (a) 109 pm (b) 127 pm

(c) Covalent crystal (d) Metallic crystal (c) 157 pm (d) 181 pm
7. Mostly crystals show good cleavage because their atoms, 16. The edge length of a face centered cubic cell of an ionic
ions or molecules are substance is 508 pm. If the radius of the cation is 110 pm,
(a) Weakly bonded together the radius of the anion is
(b) Strongly bonded together (a) 288 pm (b) 398 pm
(c) Spherically symmetrical (c) 618 pm (d) 144 pm
(d) Arranged in planes 17. An alloy of Cu, Ag and Au is found to have copper
8. Glass is constituting the ccp lattice. If silver atoms occupy the
(a) Microcrystalline solid (b) Super cooled liquid edge centre and gold is present at body centre, the alloy
has a formula
(c) Gel (d) Polymeric mixture
(a) Cu4 Ag2 Au (b) Cu4 Ag2 Au
9. In graphite, carbon atoms are joined together due to
(c) Cu4 Ag3 Au (d) CuAgAu
(a) Ionic bonding (b) Vander Waal's forces
(c) Metallic bonding (d) Covalent bonding
SOLID STATE 86
18. A compound is formed by elements A and B. This
20r 3 24r 3
crystallizes in the cubic structure when atoms A are the (a) (b)
corners of the cube and atoms B are at the centre of the 3 3
body. The simplest formula of the compounds is 12r 3 16r 3
(c) (d)
(a) AB (b) AB2 3 3
(c) A2B (d) AB2 Packing in Solids and Type of Voids
19. In a face centred cubic arrangement of A and B atoms 27. In ccp arrangement the pattern of successive layers can
when A atoms are at the corner of the unit cell and B atoms be designated as
of the face centres. One of the A atom is missing from one (a) ABABAB (b) ABCABCABC
corner in unit cell. The simplest formula of compound is
(c) ABABCAB (d) ABA ABA ABA
(a) A7B3 (b) AB3
28. The two dimensional coordination number of a molecule
(c) A7B24 (d) A7/8B3 in square close packed layer is
20. In a cubic structure of compound which is made from X
(a) 4 (b) 2
and Y, where X atoms are at the corners of the cube and Y
at the face centres of the cube. The molecular formula of (c) 3 (d) 6
the compound is 29. For the structure of solid given below if the lattice points
(a) X2Y (b) X3Y represent A+ ions & the B– ions occupy all the tetrahedral
voids then coordination number of A is
(c) XY2 (d) XY3
21. In a face centred cubic lattice, atom A occupies the corner
positions and atom B occupies the face centre positions. If
one atom of B is missing from one of the face centred points,
the formula of the compound is
(a) A2B (b) AB2
(c) A2B2 (d) A2B5
(a) 2 (b) 4
22. If the number of atoms per unit in a crystal is 2, the structure
(c) 6 (d) 8
of crystal is
30. A solid A B has the B ions arranged as below. If the A+
+ – –
(a) Octahedral (b) Body centred cubic
ions occupy half of the octahedral sites in the structure.
(c) Face centred cubic (d) Simple cubic
The formula of solid is
23. Percentage of free space in cubic close packed structure
and in body centred packed structure are respectively
(a) 30 % and 26% (b) 26% and 32%
(c) 32% and 48% (d) 48% and 26%
24. In fcc lattice, the neighbouring number of atoms for any
lattice point is
(a) 6 (b) 8
(a) AB (b) AB2
(c) 12 (d) 14
25. In a compound, atoms of element Y form ccp lattice and (c) A2B (d) A3B4
those of element X occupy 2/3rd of tetrahedral voids. The 31. In ABC ABC packing if the number of atoms in the unit
formula of the compound will be cell is n then the number of tetrahedral voids in the unit
(a) X4Y3 (b) X2Y3 cell is equal to
(a) n (b) n/2
(c) X2Y (d) X3Y4
(c) n/4 (d) 2n
26. The total volume of atoms present in face-centred cubic
unit cell of a metal is (r is atomic radius)
SOLID STATE 87
32. Which of the following statements is not true about the 39. Which of the following statements is not true about NaCl
voids? structure
(a) Octahedral void is formed at the centre of six spheres (a) Cl– ions are in fcc arrangement
which lie at the apices of a regular octahedron. (b) Na+ ions has coordination number 4
(b) There is one octahedral site for each sphere. (c) Cl– ions has coordination number 6
(c) There are two tetrahedral sites for each sphere. (d) Each unit cell contains 4NaCl molecules
(d) Octahedral voids are formed when the triangular voids 40. In CsCl structure, the coordination number of Cs+ is
in second layer exactly overlap with similar voids in the (a) Equal to that of Cl–, that is 6
first layer.
(b) Equal to that of Cl–, that is 8
Radius Ratio (c) Not equal to that of Cl–, that is 6
(d) Not equal to that of Cl–, that is 8
 rc 
33. If the value of ionic radius ratio   is 0.52 in an ionic 41. An AB2 type structure is found in
 ra 
compound, the geometrical arrangement of ions in crystal is (a) NaCl (b) CaF2
(a) Tetrahedral (b) Planar (c) Al2O3 (d) N2O
(c) Octahedral (d) Pyramidal 42. The unit cell of a NaCl lattice
34. The maximum radius of sphere that can be fitted in the (a) Is body centred cube (b) Has 3Na+ ions
tetrahedral hole of cubical closed packing of sphere of (c) Has 4NaCl units (d) Is electrically charged
radius r is.
(a) 0.732 r (b) 0.414 r Imperfection in Solids
(c) 0.225 r (d) 0.155 r 43. Schottky defect in crystals is observed when
rNa  (a) Density of crystal is increased
35. In NaCl lattice the radius ratio is = (b) Unequal number of cations and anions are missing
rCl 
from the lattice
(a) 0.225 (b) 0.115 (c) An ion leaves its normal site and occupies an interstitial
(c) 0.5414 (d) 0.471 site
36. For an ionic crystal of the general formula AX and (d) Equal number of cations and anions are missing from
coordination number 6, the value of radius ratio will be the lattice
(a) Greater than 0.73 44. In which type of point defect are the cations and anions in
stoichiometric proportions?
(b) In between 0.73 and 0.41
(a) Schottky defect
(c) In between 0.41 and 0.22
(b) Frenkel defect
(d) Less than 0.22
(c) Impurity defect
37. In A+ B– ionic compound, radii of A+ and B– ions are 180
pm and 187 pm respectively. The crystal structure of this (d) The given situation does not occur for any point defect.
compound will be 45. Which defect causes decrease in the density of crystal
(a) NaCl type (b) CsCl type (a) Frenkel (b) Schottky
(c) ZnS type (d) Similar to diamond (c) Interstitial (d) F-centre
Some important ionic crystals 46. In a Schottky defect,
38. In which compound 4 : 4 coordination is found (a) an ion moves to interstitial position between the lattice
(a) ZnS (b) CuCl points
(c) AgI (d) All of these (b) electrons are trapped in a lattice site
(c) some lattice sites are vacant
(d) some extra cations are present in interstitial spaces.
SOLID STATE 88
47. In a solid lattice the cation has left a lattice site and is (b) Oxygen and electrons move out of the crystal and ions
located at an interstitial position, the lattice defect is become yellow
(a) Interstitial defect (b) Valency defect 2+
(c) Zn again combine with oxygen to give yellow oxide
(c) Frenkel defect (d) Schottky defect
2+
48. Alkali halides do not show Frenkel defect because (d) Zn are replaced by oxygen    

(a) cations and anions have almost equal size Electrical and Magnetical Properties of Solids
(b) there is a large difference in size of cations and anions. 54. The substance which possesses zero resistance at zero
(c) cations and anions have low coordination number kelvin is called
(d) anions cannot be accommodated in voids. (a) Conductor (b) Superconductor
49. What is the effect of Frenkel defect on the density of ionic (c) Insulator (d) Semiconductor.
solids? 55. Which one among the following is an example of
(a) The density of the crystal increases. ferroelectric substance?
(b) The density of the crystal decreases. (a) Quartz (b) lead chromate
(c) The denisty of the crystal remains unchanged. (c) Barium titanate (d) Rochelle salt.
(d) There is no relationship between density of a crystal 56. The electricity produced on applying stress on the crystals
and defect present in it. is called
50. The correct statement regarding F-centre is (a) Pyroelectricity (b) Piezoelectricity
(a) Electron are held in the voids of crystals (c) Ferroelectricity (d) Anti-ferroelectricity
(b) F-centre produces colour to the crystals 57. On heating some polar crystals, weak electric current is
(c) Conductivity of the crystal increases due to F- centre produced. It is termed as :
(d) All of these (a) piezoelectricity (b) pyroelectricity
51. If a electron is present in place of anion in a crystal lattice, (c) photoelectric current (d) superconductivity
then it is called
58. Pure silicon and germanimum behave as
(a) Frenkel defect (b) Schottky defect
(a) conductors (b) semiconductors
(c) Interstitial defect (d) F-centre
52. What type of crystal defect is indicated in the diagram (c) insulators (d) piezoelectric crystals.
shown below ? 59. Which substance acts as superconductor at 4 K?
+ – +
Na Cl Na Cl Na Cl– + – (a) Hg (b) Cu
(c) Na (d) Mg
Cl– Cl– Na+ Na+
60. A solid with high electrical and thermal conductivity from
Na+ Cl– Cl–, Na+ Cl–
the following is
Cl– Na+ Cl– Na+ Na+ (a) Si (b) Li
(a) Frenkel defect (c) NaCl (d) Ice
(b) Schottky defect 61. Which substance shows antiferromagnetism?
(c) Interstitial defect (a) ZrO2 (b) CdO
(d) Frenkel and Schottky defects (c) CrO2 (d) Mn2O3
53. Zinc oxide loses oxygen on heating according to the 62. Crystals where dipoles may align themselves in an ordered
reaction, manner so that there is a net dipole moment, exhibit

heat 1 (a) Pyro-electricity (b) Piezo-electricity

ZnO   Zn 2   O2  2e
2 (c) Ferro-electricity (d) Antiferro-electricity
It becomes yellow on heating because
2+
(a) Zn ions and electrons move to interstitial sites and F-
centres are created
SOLID STATE 89
Numeric Type Questions 69. A unit cell of sodium chloride has four formula units. The
63. Sodium metal crystallizes as a body centred cubic lattice edge length of unit cell is 0.564 nm. What is the density of
with the cell edge 4.29Å. What is the radius of sodium sodium chloride?
atom. 70. Lithium forms body-centred cubic structure. The length
64. Potassium has a bcc structure with nearest neighbour of the side of its unit cell is 351 pm. Atomic radius of the
lithium will be
distance 4.52 Å. Its atomic weight is 39. Its density will be
71. Copper crystallises in fcc lattice with a unit cell edge of
65. The unit cell of aluminum is a cube with an edge length of
–3 361 pm. The radius of copper atom is
405 pm. The density of aluminium is 2.70 g cm . What is
the number of atoms in the unit cell of aluminium? 72. The number of atoms in 100 g of an FCC crystal with density
–3
66. Copper crystallizes in face centred cubic structure. The d = 10 g cm and cell edge as 200 pm is equal to
edge length of a unit cell is found to be 3.61108 cm. 73. Experimentally it was found that a metal oxide has formula
Calculate the density of copper it the molar mass of copper M0.98O. Metal M, present as M2+ and M3+ in its oxide.
is 63.5 g m ol  1 Fraction of the metal which exists as M3+ would be
67. How many lithium atoms are present in a unit cell with 74. A metal crystallises into a hexagonal lattice containing a
–3
edge length 3.5 Å and density 0.53 gcm ? (Atomic mass sequence of layer as AB AB AB ....... . What percentage of
of Li = 6.94) voids are left in the lattice?
68. An element with atomic mass 100 has a bcc structrue and 75. How many unit cells are present in a cube shaped ideal
edge length 400 pm. The density of element is crystal of NaCl of mass 1.00 g ?
(Atomic mass : Na = 23, Cl = 35.5)
SOLID STATE 90

EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS

1. Sodium metal crystallizes in a body centred cubic lattice 7. All of the following share the same crystal structure
except : Online 2018 SET (2)
with a unit cell edge of 4.29 Å. The radius of sodium atom
(a) LiCl (b) NaCl
is approximately: (2015) (c) RbCl (d) CsCl
(a) 5.72 Å (b) 0.93 Å 8. Element ‘B’ forms ccp structure and ‘A’ occupies half of
the octahedral voids, while oxygen atoms occupy all
(c) 1.86 Å (d) 3.22 Å
the tetrahedral voids. The structure of bimetallic oxide
2. Which of the following exists as covalent crystals in the is : (08-04-2019)
solid state? Online 2015 SET (1)
(a) A2B2O (b) AB2O4
(a) Silicon (b) Sulphur
(c) A4B2O (d) A4B2O
(c) Phosphorus (c) Iodine
9. Consider the bcc unit cells of the solid 1 and 2 with the
3. An element (atomic mass 100g/mol) having bcc structure position of atoms as shown below. The radius of atom B
has unit cells edge 400 pm. Then density of the element is twice that of atom A. The unit cell edge length is 50%
is : Online 2016 SET (1) more in solid 2 than in 1. What is the approximate
(a) 10.376 g/cm3 (b) 5.188 g/cm3 packing efficiency in solid 2? (08-04-2019)
(c) 7.289 g/cm3 (d) 2.144 g/cm3
4. A metal crystallises in a face centred cubic structure. If
the edge length of its unit cell is ‘a’, the closest
approach between two atoms in metallic crystal will be:
(2017)

(a) 2 2a (b) 2a
a
(c) (d) 2a (a) 90% (b) 75%
2
(c) 65% (d) 45%
5. Which type of 'defect' has the presence of cations in the
10. The statement that is INCORRECT about the interstitial
interstitial sites ? (2018)
compound is: (08-04-2019)
(a) Frenkel defect (b) Metal deficiency defect
(a) they have metallic conductivity
(c) Schottky defect (d) Vacancy defect (b) they have high melting points
6. Which of the following arrangements shows the schematic (c) they are chemically reactive
alignment of magnetic moments of antiferromagnetic
(d) they are very hard
substance ? Online 2018 SET (1)
11. An element has a face-centred cubic (fcc) structure with
(a) a cell edge of a. The distance between the centres of
two nearest tetrahedral voids in the lattice is:
(12-04-2019)
(b)
a
(a) (b) 2a
(c) 2

3
(c) a (d) a
(d) 2
SOLID STATE 91
12. The ratio of number of atoms present in a simple cubic, (c) 00137a (d) 0.067a
body centered cubic and face centered cubic structure
18. An element with molar mass 2.7 102 kg mol1
are, respectively : (12-04-2019)
forms a cubic unit cell with edge length 405 pm. If its
(a) 1 : 2 : 4 (b) 4 : 2 : 3
density is 2.7 103 kg m3 the radius of the element
(c) 4 : 2 : 1 (d) 8 : 1 : 6
13. At 100C , copper(Cu) has FCC unit cell structure with is approximately ………….. × 10–12 m (to the nearest
integer). (03-Sept-2020)
0
cell edge length x A . What is the approximate density 19. A diatomic molecule X2 has a body-centred cubic (bcc)
3
of Cu(in g cm ) at this temperature? (09-01-2019) structure with a cell edge of 300 pm. The density of the
molecule is 6.17 g cm–3. The number of molecules present
[Atomic mass of Cu = 63.55 u] in 200 g of X2 is : (Avogadro constant (NA) = 6 × 1023
mol–1) (05-Sept-2020)
205 105
(a) (b)
x3 x3 (a) 8N A (b) 2N A

211 422 (c) 40N A (d) 4N A

(c) (d)
x3 x3 20. An element crystallises in a face-centred cubic (fcc) unit
14. Which primitive unit cell has unequal edge length cell with cell edge a. The distance between the centres
(a  b  c) and all axial angles different from 90 ? of two nearest octahedral voids in the cyrstal lattice is :
(10-01-2019) (05-Sept-2020)
(a) Triclinic (b) Hexagonal a
(a) a (b)
(c) Monoclinic (d) Tetragonal 2
15. A compound of formula A 4 B3 has the hcp lattice. Which a
(c) 2a (d)
atom forms the hcp lattice and what fraction of tetrahedral 2
voids is occupied by the other atoms : (10-01-2019) 21. A crystal is made up of metal iron ' M1' and 'M 2 ' and
oxide ions. Oxide ions form a ccp lattice structure. The
2
(a) hcp lattice  A, Tetrahedral voids - B cation ' M1' occupies 50% of octahedral voids and the
3
cation 'M 2 ' occupies 12.5% of tetrahedral voids of
1 oxide lattice. The oxidation number of ' M1' and 'M 2 '
(b) hcp lattice  A, Tetrahedral voids - B are, respectively: (06-Sept-2020)
3
(a) +2, +4 (b) +3, +1
2 (c) +4, +2 (d) +1, +3
(c) hcp lattice  B, Tetrahedral voids - A
3
22. The coordination number of an atom in a body-
1 centered cubic structure is __________.
(d) hcp lattice  B, Tetrahedral voids – A [Assume that the lattice is made up of atoms]
3
(2021-02-24/Shift - 1)
16. A solid having density of 9  103 kg m 3 forms face
23. The unit cell of copper corresponds to a face centered
centred cubic crystal of edge length 200 2 pm. What cube of edge length 3.596Å with one copper atom at
is the molar mass of the solid? (11-01-2019) each lattice point. The calculated density of copper in
[Avogadro constant NA  6  10 23 mol 1 ,   3.14 ] kg/m3 is __________.
[Molar mass of Cu: 63.54 g; Avogadro Number]
(a) 0.0432 kg mol1 (b) 0.0216 kg mol1
(2021-02-25/Shift - 2)
1 1
(c) 0.0305 kg mol (d) 0.4320 kg mol 24. The number of octahedral voids per lattice site in a
17. The radius of the largest sphere which fits properly at lattice is _______. (rounded off to the nearest
the centre of the edge of a body centered cubic unit cell integer)
is: (Edge length is represented by ‘a’) (11-01-2019) (2021-02-26/Shift - 2)
(a) 0.0027a (b) 0.047a
SOLID STATE 92
25. A certain element crystallises in bcc lattice of unit cell 32. A hard substance melts a at high temperature and is an
edge length 27 Å . If the same element under the same insulator in both solid and in molten state. This solid
conditions crystallises in the fcc lattice, the edge is most likely to be a/an: (2021-03-18/Shift - 2)
length of the unit cell will be ________. (Round off to (a) Covalent solid (b) Molecular solid
the nearest integer). (c) Ionic solid (d) Metallic solid
[Assume each lattice point has a single atom] 33. Select the correct statements.
[Assume 3  1.73, 2  1.41 ] (A) Crystalline solids have long range order.
(2021-03-16/Shift - 1) (B) Crystalline solids are isotropic.
26. Ga (atomic mass 70u) crystallizes in a hexagonal close (C) Amorphous solid are sometimes called pseudo
packed structure. The total number of voids in 0.581 g solids.
of Ga is ______ × 1021. (Round off to the nearest (D) Amorphous solids soften over a range of
integer). temperatures.
[Given: NA = 6.023 × 1023] (E) Amorphous solids have a definite heat of fusion.
(2021-03-16/Shift - 2) Choose the most appropriate answer from the options
27. KBr is doped with 10–5 mole percent of SrBr2. The given below. (2021-07-27/Shift - 2)
number of cationic vacancies in 1 g of KBr crystal is (a) (A), (B), (E) only (b) (B), (D) only
__________ × 1014. (Round off to the nearest integer) (c) (C), (D) only (d) (A), (C), (D) only
[Atomic mass: K: 39.1 u, Br: 79.9 u NA = 6.023 × 1023]
34. The parameters of the unit cell of a substance are a =
(2021-03-17/Shift - 2)
2.5, b = 3.0, c = 4.0,     90º ,   120º . The
28. Dimond has a three-dimensional structure of C atoms crystal system of the substance is:
formed by covalent bonds. The structure of diamond
(2021-07-27/Shift - 1)
has face centred cubic lattice where 50% of the
tetrahedral voids are also occupied by carbon atoms. (a) Hexagonal (b) Orthorhombic
The number of carbon atoms present per unit cell of (c) Monoclinic (d) Triclinic
diamond is ________. (2021-07-27/Shift - 2) 35. Given below are two statements:
29. A copper complex crystallizing in a CCP lattice with a Statement I: Frenkel defects are vacancy as well as
cell edge of 0.4518 nm has been revealed by employing
interstitial defects.
x-ray diffraction studies. The density of a
Statement II: Frenkel defect leads to colour in ionic
copper complex is found to be 7.62 g cm–3. The molar
solids due to presence of F-centers.
mass of copper complex is _______ g mol–1. (Nearest
integer) Choose the most appropriate answer for the
statements from the option given below:
[Given: NA = 6.022 × 1023 mol–1]
(2021-08-26/Shift - 1)
(2021-07-22/Shift - 2)
(a) Statement I is false, but statement II is true
30. The empirical formula for a compound with a cubic
close packed arrangement of anions and with cations (b) Both statement I and statement II are true
occupying all the octahedral sites in AXB. The value (c) Statement I is true, but statement II is false.
of x is _______. (Integer answer) (d) Both statement I and statement II are false.
(2021-08-31/Shift - 2)
31. In a binary compound, atoms of element A form a hcp
structure and those of element M occupy 2/3 of the
tetrahedral voids of the hcp structure. The formula of
the binary compound is: (2021-03-18/Shift - 1)
(a) M2A3 (b) M4A3
(c) M4A (d) MA3
SOLID STATE 93

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only One Correct Option] 7. Frenkel defect is caused due to
(a) An ion missing from the normal lattice site creating
1. If an atom is present in the centre of the cube, the
participation of that atom per unit cell is a vacancy

1 (b) An extra positive ion occupying an interstitial

(a) (b) 1
4 position in the lattice
1 1 (c) An extra negative ion occupying an interstitial
(c) (d)
2 8 position in the lattice
2. The number of octahedral voids in a unit cell of a (d) The shift of a positive ion from its normal lattice
cubical closest packed structure is
site to an interstitial site
(a) 1 (b) 2
8. Ionic solids, with Schottky defects, contain in their
(c) 4 (d) 8 structure
3. The number of tetrahedral voids in a unit cell of (a) Equal number of cation and anion vacancies
cubical closest packed structure is
(b) Anion vacancies and interstitial anions
(a) 1 (b) 2
(c) Cation vacancies only
(c) 4 (d) 8
(d) Cation vacancies and interstitial cations
4. A metal crystallizes in a face-centered unti cell. Its
9. Which of the following is an example of covalent crystal
edge length is 0.410 nm. The radius of the metal is
solid
(a) 0.205 nm (b) 0.290 nm
(a) Si (b) NaF
(c) 0.145 nm (d) 0.578 nm
(c) Al (d) Ar
5. If ‘a’ stands for the edge length of the cubic systems:
simple cubic, body centred cubic and face centred 10. Which of the following is an example of metallic crystal
cubic, then the ratio of radii of the spheres in these solid
systems will be respectively. (a) C (b) Si

(a) 1a : 3a : 2a (c) W (d) AgCl

11. Which of the following is an example of ionic crystal
1 3 1 solid
(b) a: a: a
2 4 2 2 (a) Diamond (b) LiF
(c) Li (d) Silicon
1 1
(c) a : 3a : a 12. What is the coordination number of sodium in Na2O
2 2
(a) 6 (b) 4
1 3 2 (c) 8 (d) 2
(d) a: a: a
2 2 2 13. A metallic element has a cubic lattice. Each edge of the
unit cell is 2 Å. The density of the metal is 2.5 g cm–3 .
6. Which one of the following defects does not affect
The unit cells in 200 g of the metal are
the density of the crystal ?
(a) 1 × 1025 (b) 1 × 1024
(a) Schottky defect (b) Interstitial defect
(c) 1 × 1022 (d) 1 × 1020
(c) Frenkel defect (d) Both b and c
SOLID STATE 94
–3
14. The density of KBr is 2.75 g cm . The length of the unit 21. If the coordination number of Ca2+ in CaF2 is 8, then
cell is 654 pm. Atomic mass of K = 39, Br = 80. Then the the coordination number of F– ion would be
solid is
(a) 3 (b) 4
(a) Face centred cubic
(c) 6 (d) 8
(b) Simple cubic system
22. Potassium fluoride has NaCl type structure. What is
(c) Body centred cubic system the distance between K+ and F– ions if cell edge is a cm
(d) None of these (a) 2 a cm (b) a/2 cm
15. In octahedral holes (voids) (c) 4a cm (d) a/4 cm
(a) A simple triangular void surrounded by four spheres 23. The structure of MgO is similar to NaCl. What would
(b) A bi-triangular void surrounded by four spheres be the coordination number of magnesium.
(c) A bi-triangular void surrounded by six spheres (a) 2 (b) 4
(d) A bi-triangular void surrounded by eight spheres (c) 6 (d) 8
16. For the structure given below the site marked as S is a 24. In the crystals, which of the following ionic compounds
would you expect maximum distance between centres
of cations and anions
(a) LiF (b) CsF
(c) CsI (d) LiI
+ –
25. A solid A B has a body centred cubic structure. The
distance of closest approach between the two ions is
(a) Tetrahedral void (b) Cubic void
0.767 Å. The edge length of the unit cell is
(c) Octahedral void (d) None of these
17. The coordination number of a metal crystallizing in a 3
(a) pm (b) 142.2 pm
hexagonal close packed structure is 2
(a) 4 (b) 12
(c) 2 pm (d) 88.56 pm.
(c) 8 (d) 6
18. A binary solid x+ y– has a zinc blende structure with y– 26. An oxide of transition metal that has conductivity as
ions forming the lattice and x+ ion occupying 25% well as appearance like that of copper is
tetrahedral sites. The formula of the solid is (a) Ti2O3 (b) V2O3
(c) ReO3 (d) Mn2O3
(a) xy (b) x2y
27. The oxide that is insulator is
(c) xy2 (d) xy4
(a) VO (b) CoO
19. The number of formula unit in unit cell of CsCl, type is
(c) ReO3 (d) Ti2O3
(a) 1 (b) 2
28. Which of the following is ferromagnetic?
(c) 3 (d) 4
(a) Ni (b) Co
20. The interionic distance for caesium chloride crystal will
(c) Fe3O4 (d) All are correct.
be
a
(a) a (b)
2
3a 2a
(c) (d)
2 3
SOLID STATE 95
29. For a solid with the following structure, the co- 35. Ferrous oxide has a cubic structure and each edge of
ordination number of the point B is the unit cell is 5.0 Å. Assuming density of the oxide as
4.0 g cm–3, then the number of Fe2+ and O2– ions present
in each unit cell will be
(a) Four Fe2+ and four O2– (b) Two Fe2+ and four O2–
(c) Four Fe2+ and two O2– (d) Three Fe2+ and three O2–
Objective Questions II
(a) 3 (b) 4 [One or more than one correct option]
(c) 5 (d) 6
36. Which of the following systems do not give correct
30. The percentage of iron present as Fe(III) in Fe0.93O1.0 is description of axial lengths and axial angles ?
(a) 17.7% (b) 7.84% (a) Hexagonal : a = b  c,     90º ,   120º
(c) 11.5% (d) 9.6%
(b) Trigonal : a = b  c,     90º ,   90º
31. Potassium has a bcc structure with nearest neighbour
distance 4.52 Å. Its atomic weight is 39. Its density (c) Monoclinic : a  b  c,       90º
(in kg m–3) will be
(a) 454 (b) 804 (d) Cubic : a = b  c,       90º
(c) 852 (d) 911 37. Graphite is
32. The following structure drawn is of (a) a good conductor (b) sp3 hybridized
(c) an amorphous solid (d) soft and slippery
38. Diamond is
(a) a covalent solid (b) non-conductor
(c) soft and slippery (d) sp2 hybridized
(a) Fluorite (b) Caesium chloride
39. Crystal systems in which no two axial lengths are equal
(c) Wurtzite (d) Zinc blende
are
33. A sample of electrically neutral NaCl crystal is analysed
(a) triclinic (b) orthorhombic
for its density which has some unoccupied sites. Two
readings where taken. (c) monoclinic (d) tetragonal
1. Density of NaCl crystal assuming all sites are occupied 40. Which of the following are not true about hexagonal
= 2.178 × 103 kg m–3 close packing ?
2. Density of NaCl crystal by not considering the (a) It has a coordination number of 6.
unoccupied sites but only the occupied sites = 2.165 × (b) It has 26% empty space.
103 kg m–3. (c) It has ABAB..... type of arrangement
The percentage of unoccupied sites in NaCl crystal is (d) It is as closely packed as body-centered cubic
(a) 5.96 × 10–2 (b) 5.96 × 10–1 packing
(c) 5.96 (d) 8.68 41. Which of the following statements are true ?
3+ +
34. If Al ions replace Na ions at the edge centres of (a) An element with bcc structure has two atoms per
NaCl lattice, then the number of vacancies in 1 mole of unit cell.
NaCl will be (b) An ionic compound A+B– with bcc structure has
23 23
(a) 3.01 × 10 (b) 6.02 × 10 one AB formula unit per unit cell.
23 23
(c) 9.03 × 10 (d) 12.04 × 10 (c) The shape of the octahedral void is octahedral.
(d) The edge length of the crystal A+B– is equal to the
distance between A+ and B– ions.
SOLID STATE 96
42. The coordination number of anion is 4n Numerical Value Type Questions
(a) sodium chloride (b) zinc chloride
48. Sodium crystallizes in a bcc cubic lattice with the cell
(c) caesium chloride (d) calcium fluoride edge, a = 4.29 Å. What is the radius of sodium atom ?
43. Which of the following are true ? 49. A metal crystallizes into two cubic phases, face centred
+
(a) In NaCl crystals, Na ions are present in all the cubic (fcc) and body centred cubic (bcc), whose unit
octahedral voids. cell lengths are 3.5 and 3.0 A, respectively, Calculate
the ratio of densities of fcc and bcc.
(b) In ZnS (zinc blende), Zn2+ ions are present in
alternate tetrahedral voids. 50. A metal X crystallizes in a unit cell in which the radius
of atoms (r) is related to edge of unit cell (a) as r =
(c) In CaF2, F– ions occupy all the octahedral voids. 0.3535a. The total number of atoms present per unit cell
(d) In Na2O, O2– ions occupy half of the octahedral is _____.
voids. 51. A cubic unit cell has one atom on each corner and one
44. The coordination number of 8 for cation is found in atom on each body diagonal. The number of atoms in
(a) CsCl (b) NaCl the unit cell is _____ .
52. Atoms of element A form hcp arrangement and those of
(c) CaF2 (d) Na2O
element B occupy 2/3rd of tetrahedral voids. The total
45. Which of the following statement are correct ? number of A and B per formula unit is ______.
(a) The coordination number each type of ion in CsCl 53. In hexagonal close packing, the difference in the number
crystal is 8.
of tetrahedral and octahedral voids in a unit cell is ____.
(b) A metal that crystallizes in bcc structure has
54. Chromium metal crystallizes with a body centred cubic
coordination number of 12.
lattice. The length of the unit edge is found to be 287
(c) A unit cell of an ionic crystal shares some of its ions pm. Calculate the atomic radius. What would be the
with other unit cells. density of chromium in g/cm3 ?
(d) The length of the edge of unit cell of NaCl is 552 pm
55. The radius ratio of an ionic solid r+/r– is 0.524. The
( rNa  = 95 pm, rCl = 181 pm) coordination number of this type of structure is ____.
46. The correct statement(s) regarding defects in solids is 56. NH4+ and Br– ions have ionic radii of 139 pm and 186
(are) pm, respectively. The coordination number of NH4+ ion
(a) Frenkel defect is usually favoured by a very small in NH4Br is _____ .
difference in the sizes of cation and anion. 57. Al3+ ions replace Na+ ions at the edge centers of NaCl
(b) Frenkel defect is a dislocation defect lattice. The number of vacancies in one mole NaCl is
(c) Trapping of an electron in the lattice leads to the calculated as n × 10 23. The value of n approximately
formation of F-center is __.

(d) Schottky defects have no effect on the physical

properties of solids.
47. Which of the following statements are not true ?
(a)The conductivity of metals increases with increase
in temperature.
(b) Electrical conductivity of semiconductors increases
with increase in temperature.
(c) A diode is a combination of conductor and a
semiconductor.
(d) V2O5 behave as an insulator.
SOLID STATE 97
Assertion Reason 64. Assertion (A) : Size of tetrahedral void is much larger
(A) If both Assertion and Reason are correct and than an octahedral void.

reason is the correct explanation of assertion. Reason (R) : The cations may occupy more space than
anions in crystal packing.
(B) If both Assertion and Reason are true but reason
is not the correct explanation of assertion. (a) A (b) B

(C) If Assertion is true but reason is false. (c) C (d) D

(D) If Assertion is false but reason is true. 65. Assertion (A) : Zinc blende and wurtzite both have fcc
arrangement of sulphide ions.
58. Assertion (A) : The number of tetrahedral voids is
Reason (R) : There are four formula units of ZnS in
double the number of octahedral voids.
both.
Reason (R) : The size of the tetrahedral void is half of
(a) A (b) B
that of the octahedral void.
(c) C (d) D
(a) A (b) B
66. Assertion (A ) : In CaF2, F– ions occupy all the
(c) C (d) D
tetrahedral sites.
59. Assertion (A) : Due to Frenkel defect there is no effect
Reason (R) : The number of Ca2+ is double the number
on density of a solid.
of F– ions.
Reason (R) : Ions shift from lattice sites to interstitial
sites in Frenkel defect. (a) A (b) B

(a) A (b) B (c) C (d) D

(c) C (d) D 67. Assertion (A) : In ZnO, the excess Zn2+ ions are present
in interstitial sites.
60. Assertion (A) : Crystalline solids are anisotropic.
Reason (R): Metal excess crystals have either missing
Reason (R) : The constituent particles are very closely
cation or anion in interstitial site.
packed.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
68. Assertion (A) : Antiferromagnetic substances become
61. Assertion (A) : Ionic crystals have the highest melting
paramagnetic on heating to high temperature.
point.
Reason (R) : Heating results in spins of electrons
Reason (R) : Covalent bonds are stronger than ionic
becoming random.
bonds.
(a) A (b) B
(a) A (b) B
(c) C (d) D
62. Assertion (A) : Graphite is an example of tetragonal
crystal system.
Reason (R) : For a tetragonal system, a = b  c,  =  =  =
90º.
(a) A (b) B
(c) C (d) D
63. Assertion (A) : Triclinic system is the most
unsymmetrical system.
Reason (R) : All axial lengths are different in a triclinic
system.
(a) A (b) B
(c) C (d) D
SOLID STATE 98
(c) C (d) D (c) 3.86 × 10–23 cm3 (d) None of these
Match the following 72. An element X crystallizes in a structure having an fcc
Each questions has two columns. Four optionsare unit cell of an edge 100 pm. If 24 g of the element contains
given representing matching elements from 24 × 1023 atoms, the density is
Column-I and Column-II. Only one of these four (a) 2.40 g cm–3 (b) 40 g cm–3
options corresponds to a correct matching. For (c) 4 g cm–3 (d) 24 g cm–3
each questions, choose the correct option corre- 73. The number of atoms present in 100 g of a bcc crystal
sponding to the correct matching. (density = 12.5 g cm–3) having cell edge 200 pm is
69. Match the types of solid with their examples/properties. (a) 1 × 1025 (b) 1 × 1024
Column - I Column - II (c) 2 × 1024 (d) 2 × 1026
(A) Molecular solid (p) Dry ice Use the following passage, solve Q.74 to Q.76
(B) Covalent solid (q) Copper Passage
(C) Metallic solid (r) Generally behave as
X-ray studies show that the packing of atoms in a crystal
insulators
of a metal is found to be in layer such that starting from
(D) Ionic solid (s) Generally have low any layer, every fourth layer is exactly identical. The
melting points density of the metal is found to be 19.4 g cm–3 and its
70. Match the type of packing with the metal possessing atomic mass is 197 u.
it/space occupied.
74. The fraction occupied by metal atoms in the crystal is
Column - I Column - II
(a) 0.52 (b) 0.68
(A) Body-centered cubic (p) Iron
(c) 0.74 (d) 1.0
(bcc)
75. The length of the edge of the unit cell will be
(B) Hexagonal cubic (q) 52%
(a) 407 pm. (b) 189 pm.
(C) Cubic close packing (r) 68%
(c) 814 pm. (d) 204 pm.
(D) Simple cubic (s) 74%
76. Assuming the metal atom to be spherical, its radius will
Pragraph type questions be
Use the following passage, solve Q.71 to Q.73 (a) 103.5 pm. (b) 143.9 pm.
Passage
Density of a unit cell is the same as the density of the
substances. So, if the density of the substance is known,
we can calculate the number of atoms or dimesions of
the unit cell. The density of the unit cell is related to its
mass (M), number of atoms per unit cell (Z), edge length
(a in cm), and Avogadro’s constant NA as :

Z M

a3  NA

71. A metal A (atomic mass = 60) has a body - centered

cubic crystal structure. The density of the metal is 4.2 g
cm–3. The volume of unit cell is
(a) 8.2 × 10–23 cm3 (b) 4.72 × 10–23 cm3
SOLID STATE 99
(c) 146.5 pm. (d) 267.8 pm. (c) 6, 8 (d) 4, 6
Use the following passage, solve Q.77 to Q.78 Use the following passage, solve Q.79 to Q.80
Passage Passage

Crystalline solids have an ordered internal arrangement Crystals as such are never perfect and in general have
of atoms due to which they exhibit symmetry. The atoms some defect, which simply refers to a disruption in the
are arranged in a symmetrical fashion in the three- periodic order of a crystalline material. Based on their
dimensional network known as space lattice. Each point nature, these are classified into three types :
in a crystal lattice is known as lattice point or lattice stoichiometric, impurity and non-stoichiometric defects.
site. In non-stoichiometric defects, the ratio of the number
of atoms of one kind to the number of atoms of the
Each point in a crystal lattice represents a constituent
other kind does not correspond exactly to the ideal whole
particle which can be an atom, ion or a molecule. The
number ratio implied by the formula. For example, the
smallest repeating subunit in the lattice is known as
ideal formula of ferrous oxide should be FeO, but it is
unit cell. The unit cells are described as simple (points
actually found to be Fe0.93O in a sample, because some
at all the corners), body-centered (points at all the
ferric ions have replaced ferrous ions in the crystal.
corners and in the center), face-centered (points at all
These defects affect the properties of the crystals.
the corners and center of all faces), and end-centered
Sometimes such defects are introduced to improve the
(points at all the corners and centers of two opposite
properties of the crystals for a specific use, such as in
end faces) unit cells. For the stable ionic crystalline
the field of electronics. Elements of Group 14 are
structures, the radius ratio limit for a cation to fit perfectly
commonly doped with impurities of elements of Group
in the lattice of anions is determined by the radius ratio
13 or 15. In ionic crystals, impurities are introduced with
rule. This also defines the number of nearest neighbours
cations having higher valence than the cations in the
of opposite charges surrounding the ion, which is
known as the coordination number. This depends upon pure crystal structure.
the ratio of radii of two types of ions, r+/r–. The radius 79. Which one of the following doping will produce p-type
ratios for coordination numbers 3, 4, 6 and 8 are 0.155 – semi-conductor ?
0.225–0.414, 0.414–0.732 and 0.732–1, respectively. The (a) Silicon doped with arsenic
coordination number of ionic solids increases with
(b) Germanium doped with phosphorus
increase in pressure and decreases with increase in
(c) Germanium doped with aluminium
temperature.
(d) Silicon doped with phosphorus
77. In a cubic lattice of ABC, A atoms are present at all
corners except one corner which is occupied by B atoms. 80. NaCl was doped with 10 –3 mol % SrCl 2 . The
C atoms are present at face centers. The formula of the concentration of cation vacancies is
compound is (a) 6.02 × 1018 mol–1 (b) 6.02 × 1015 mol–1
(a) A8BC24 (b) ABC3 (c) 6.02 × 1021 mol–1 (d) 6.02 × 1012 mol–1
(c) A7B24C (d) A7BC24
78. The ionic radii of Na+, K+ and Br– are 137, 148 and 195
pm, respectively. The coordinaiton number of cation in
KBr and NaBr structures are, respectively,
(a) 8, 6 (b) 6, 4
SOLID STATE 100

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

1. In a solid ‘AB’ having the NaCl structure, ‘A’ atoms occupy Comprehension (Ques. 7 to 9)
the corners of the cubic unit cell. If all the face-centred In hexagonal systems of crystals, a frequently encountered
atoms along one of the axes are removed, then the resultant arragenement of atoms is described as a hexagonal prism.
stoichiometry of the solid is (2001) Here the top and bottom of the cell are regular hexagons
and three atoms are sandwiched in between them. A space-
(a) AB2 (b) A2B
filling model of this structure, called hexagonal close-
(c) A4B3 (d) A3B4 packed (HCP), is constituted of a sphere on a flat surface
2. The crsytal AB (rock salt structure) has molecular weight surrounded in the same plane by six identical spheres as
6.023 y u. where, y is an arbitrary number in u. If the mini- closely as possible. Three spheres are then placed over
mum distance between cation and anion is y1/3 nm and the the first layer so that they touch each other and represent
observed density is 20 kg/m3. Find the (a) density in the second layer. Each one of these three spheres touches
kg/m3 and (b) type of defect (2004) three spheres of the bottom layer. Finally, the second layer
is covered with a third layer that is identical to the bottom
3. An element crystallizes in fcc lattice having edge length layer that is identical to the bottom layer in relative position.
400 pm. Calculate the maximum diameter of atom which Assume radius of every sphere to be ‘r’. (2008)
can be placed in interstitial site without distorting the
7. The number of atoms on this HCP unit cell is :
structure. (2005)
(a) 4 (b) 6
4. Which of the following fcc structure contains cations in (c) 12 (d) 17
alternate tetrahedral voids ? (2005) 8. The volume of this HCP unit cell is :
(a) NaCl (b) ZnS
(a) 24 2 r 3 (b) 16 2r3
(c) Na2O (d) CaF2

5. The edge length of unit cell of a metal having molecular 64r 3

(c) 12 2 r 3 (d)
weight 75 g/mol is 5 Å which crystallizes in cubic lattice. If 3 3
the density is 2 g/cc then find the radius of metal atom.
9. The empty space in this HCP unit cell is :
(NA = 6 × 1023). Give the answer in pm. (2006)
(a) 74% (b) 47.6%
Match the Column (c) 32% (d) 26%
6. Match the crystal system/unit cells mentioned in Column- 10. If the unit cell of a mineral has cubic close packed (ccp)
I with their characteristic features mentioned in Column-II.
array of oxygen atoms with m fraction of octahedral holes
Indicate your answer by darkening the appropriate bubbles
occupied by aluminium ions and n fraction of tetrahedral
of the 4 × 4 matrix given in the ORS. (2007)
holes occupied by magnesium ions, m and n, respectively,
Column I Column II
(A) Simple cubic and (p) have these cell are (2015)
face-centred cubic parameters a = b = c and 1 1 1
(a) , (b) 1,
   2 8 4
(B) Cubic and (q) are two crystal 1 1 1 1
(c) , (d) ,
rhombohedral systems 2 2 4 8
(C) Cubic and tetragonal (r) have only two
crystallographyangles of 90º
(D) Hexagonal and (s) belong to same
monoclinic crystal system
SOLID STATE 101
11. The Correct statement(s) for cubic close packed (ccp) three 15. For the given close packed structure of a salt made of
dimensional structure is (are) (MCQ)(2016) cation X and anion Y shown below (ions of only one
(a) The number of the nearest neighbours of an atom face are shown for clarity), the packing fraction is
present in the topmost layer is 12 packing efficiency
(b) The efficiency of atom packing is 74% approximately (packing fraction  ).
100
(c) The number of octahedral and tetrahedral voids per (2021)
atom are 1 and 2, respectively
(d) The unit cell edge length is 2 2 times the radius of
the atom
12. A crystalline solid of a pure substance has a face-centred
cubic structure with a cell edge of 400 pm. If the density of
the substance in the crystal is 8 g cm–3, then the number of
atoms present in 256 g of the crystal is N × 1024. The value
of N is (2017)

13. Consider an ionic solid MX with NaCl structure. Construct

a new structure (Z) whose unit cell is constructed from the
unit cell of MX following the sequential instructions given
below. Neglect the charge balance. (2018)
(i) Remove all the anions (X) except the central one (a) 0.74 (b) 0.63
(ii) Replace all the face centered cations (M) by anions (X) (c) 0.52 (d) 0.48
(iii) Remove all the corner cations (M)
(iv) Replace the central anion (X) with cation (M)
 number of anions 
The value of   in Z is ..........
 number of cations 
14. The cubic unit cell structure of a compound containing
cation M and anion X is shown below. When compared
to the anion, the cation has smaller ionic radius. Choose
the correct statement(s). (MCQ)(2020/Paper 1)

(a) The empirical formula of the compound is MX.

(b) The cation M and anion X have different
coordination geometries.
(c) The ratio of M-X bond length to the cubic unit cell
edge length is 0.866.
(d) The ratio of the ionic radii of cation M to anion X is
0.414.
SOLID STATE 102

Note:

Find Answer Key and Detailed Solutions at the end of this book

SOLID STATE

Please share your valuable feedback by

scanning the QR code.
GENERAL ORGANIC CHEMISTRY
(REVISION) & ISOMERISM
 Chapter 03 104

GENERAL ORGANIC CHEMISTRY

(REVISION) & ISOMERISM

1. INTRODUCTION NOTE
The making and breaking of bonds usually occurs in several
In 1807, Berzelius proposed the term ‘Organic Chemistry’ for the discrete steps before transforming into products. The detailed
study of compounds derived from natural sources. This was based sequential description of all the steps is called the mechanism
on the theory of vitalism which said that all living systems of the reaction.
possessed a ‘vital force’ which was absent in non-living systems.
Compounds derived from living natural sources (organic) were 2. HYBRIDIZATION
thought to be fundamentally different from inorganic compounds.
Hybridisation is a process in which two or more atomic orbitals of
comparable energy of the valence-shell of an atom (central atom
of the molecule or ion) either in its ground state or in its excited
state mix together and give rise to the formation of new degenerate
orbitals which are called hybrid orbitals.
The vital force could be philosophically thought as the mysterious
force God instilled in the living systems. Hybridization % s-character
In 1823, Friedrich Wohler joined Berzelius as his student. In 1828, sp 3 25.0
Wohler made a discovery which changed the definition of organic sp 2
33.3
chemistry. Wohler conducted the following experiment.
sp 50.0

2.1 Applications of Hybridization

 Size of Hybrid Orbitals

Wohler successfully synthesized an organic compound starting As % s-character increases, size of hybrid orbital decreases.
from an inorganic compound. Following this, many others Therefore
synthesized organic compounds starting from inorganic 3 2
compounds. Thus, the theory of vitalism and the definition of Size of Hybrid Orbital : sp > sp > sp
organic chemistry lost its meaning.  Electronegativity of Hybrid Orbitals
But what was common in all the above compounds synthesized As % s-character increases, electronegativity of hybrid orbital
was the presence of carbon. Carbon shows a special property increases. Therefore
catenation. Carbon can connect with other carbon atoms to form 2 3
EN of Hybrid Orbital : sp > sp > sp
long chains and rings (self-catenation) and can connect with atoms 2.2 Dienes
of many other elements in the periodic table (cross-catenation).
Because of this reason, carbon can form a wide variety of Dienes are organic compounds containing two double bonds.
compounds. Therefore, the modern definition of organic There are three types of dienes :
chemistry is the study of carbon compounds. (a) Isolated (b) Conjugated (c) Cumulated
Probably, the vital force can be explained by the fact that most of (a) Isolated Diene :
the life-giving and life-sustaining functions are performed by 3
In this case, double bonds are separated by atleast one sp carbon.
carbon compounds, for example, the human tissues and skin are
formed by proteins, respiration is possible due to haemoglobin,
the information in our genes is carried out in the form of DNA/
RNA etc.
General Organic Chemistry is the detailed study of the basic
concepts and factors that govern the progress and outcome of
reactions.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 105

Hybridization of Common Molecules

(b) Conjugated Diene : (A) Characterstics of Inductive Effect

2
Double bonds are separated by only one single bond (or 4 sp
carbons in a row).

(c) Cumulated Diene :

Both sets of double bonds are at the same carbon. There are broadly three types of groups/atoms that may be
attached to carbon as illustrated. Although C is more
electronegative than H, the electronegativity difference is small
A substituted allene
and the bond is generally consider non-polar.
An allene is
Stability of Dienes :  Nature of Inductive Effect
The relative stabilities of dienes follows the order Inductive effect is a permanent effect and can be directly
Conjugated > Isolated > Cumulated correlated to its dipole moment.
Important : It is a weak effect as the shifting of electrons takes place only
through sigma bonds.
1
Stability 
Energy Content of the molecule  Effect of branched carbon chain
An illustration has been marked for operation of inductive effect
3. ELECTRONIC DISPLACEMENT EFFECT which is self-explanatory.

More the number of , lesser the effect

3.1 Inductive effect  Electron Donating and Electron withdrawing Groups

When two unlike atoms form covalent bond, the electron-pair Inductive effect may be due to single atom or a group of atoms.
forming the sigma bond is never shared equally between the two Relative inductive effects are measured with reference to hydrogen.
atoms but is shifted slightly towards the more electronegative Those which donate electrons to carbon chain are called electron-
species. donating groups (EDG) or electron-releasing groups (ERG) and
are said to exert +I effect. Those which withdraw electrons from
carbon chain are called electron-withdrawing groups (EWG) and
are said to exert –I effect.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 106
Important : Example
1. I.E. of alkyl groups : 3° > 2° > 1° > –CH3
(a) Compare the acidic strength of :
2. In general, greater is the number of carbons in an alkyl group,
greater is its +I effect. (I)

3. For problem-solving, we take electronegativity of sp-hybridized (II)

3
carbon to be more than sp hybridized nitrogen.
(B) Applications of Inductive Effect
(III)
 Effect on Acidic/Basic Strength
EWG increases acidic strength and decreases basic strength. ERG
decreases acidic strength and increases basic strength. (IV)
Example

Compare the acidic strength : Solution :

(I) (II) (a) (I)

(II)
(III)

Solution :
An alkyl group is donating only if no other EWG is present on it. (III)
Therefore, groups like –CH2Cl and –CH2F become electron
withdrawing groups.
Order of Acidic Strength : III > II > I
 Effect of Distance (IV)
If the ERG/EWG moves away, the inductive effect diminishes.

Order of acidic strength : II > III > IV > I

Series of +I and –I groups in order of their strength

–I Series (EWG)

+I Series (ERG)

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 107
 Basicity of Amines (4) Pi alternate Odd Electron :

The order in gaseous or liquid phase is : Example

3° > 2° > 1° > NH3
To determine the basic strength of amines in aqueous phase. We
have to consider inductive effect, solvation effect and steric
hinderance. The order of basic strength is therefore experimental (5) Pi alternate Lone Pair :
in aqueous state as we can’t give priority to stability provided by This case is similar to ‘pi alternate negative charge’ as lone pair
any one factor. Two results are important for aqueous phase : and negative charge are treated similarly.
(a) (CH3)2NH > CH3NH2 > (CH3)3N > NH3 Example
i.e. 2° > 1° > 3° > NH3 (R = CH3)
(b) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
i.e. 2° > 3° > 1° > NH3 (R = C2H5)
3.2 Resonance

Molecules are generally represented by simple lewis structures

but some molecules can not be represented by just one Lewis
structure. This led to the discovery of resonance. Resonance refers (6) Lone Pair and Positive Charge on Adjacent Atoms
to the delocalization of electrons (generally -electrons).

(A) Conjugated Systems Example

(1) Pi alternate Pi bond : (B) Rules for Validity of Lewis Structures

Example
Rule-1 :
All the lewis structures must conform to lewis octet rule.

Rule-2 :
Position of atoms in all resonating structures must be the same.
Only the electrons move.
Rule-3 :
All the resonating structures must have the same number of paired
and unpaired electrons, i.e. sum of bond pairs and lone pairs must
be constant.
Rule-4 :
(2) Pi alternate Positive Charge : All the atoms participating in resonance in a molecule must be
coplanar. This is required for the effective overlap of p orbitals
Example and the delacalization of electrons, for eg, buta-1, 3-diene.

(C) Criteria for Major/Minor Contributors

Resonance forms can be compared using the following criteria in

the following order :
1. Complete octet (a neutral molecule is always more stable in
(3) Pi alternate Negative Charge : which its octet is complete).
2. More number of  bonds more will be stability.
Example
3. Negative charge on more electronegative atom is stable.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 108
(D) Charge separation Solution :
In (I), there are maximum number of pi bonds. Therefore, it is most
1. Similar charges - Keep them as FAR as possible to
stable. In (II) and (V), the number of pi bonds is equal but charge
minimize repulsion and instability.
separation is greater in (V). Therefore, (II) is more stable than (V). In
2. Opposite charges - Keep them as NEAR as possible to maximize (III) and (IV), there is maximum charge separation but (III) is highly
attraction and stability. unstable due to electrostatic repulsion. Hence, the order of stability
Example is :
I > II > V > IV > III
Which of the following structures is more stable ?
3.3 Mesomeric Effect

The permanent polarization, due to a group conjugated with a 

bond or a set of alternate bonds, is transmitted through the 
Solution : electrons of the system-resulting in a different distribution of
II is more stable as all the octets are complete. electrons in the unsaturated chain.
Example This kind of electron redistribution in unsaturated compounds
conjugated with electron-releasing or electron-withdrawing groups
Which of the following is more stable in the following pairs ? (or atoms) is called Mesomeric Effect or Resonance Effect.
This effect is permanent and is indicated by the dipole moment.
(a)
(a) Electron-Releasing and Electron-Withdrawing Groups

Groups which release or withdraw electrons by resonance are said

to exert M or R effect.
 Electron-Releasing Groups (+R or +M effect)
(b)
The common thing about all the groups listed is that the atom
connected with the conjugated system has a lone pair to donate.
Solution : Therefore, a generic representation can be
(a) In II, all octets are complete. Therefore, II is more stable.  Electron-Withdrawing Groups (–R or –M effect)
(b) I and II are tied on octets and number of  bonds but negative
charge is more stable on more electronegative atom. Hence, II is
more stable. The common thing about all the groups listed is that the
atom connected with the conjugated system has a  bond with
Example
another more electronegative atom which withdraws the electrons
Give the order of stability of following resonating structures or directly has a positive charge on them. Therefore, a generic
(I) representation can be (ENZ > ENY)
 Dual Behaviour
(II) Groups such as are both electron-releasing and
electron-withdrawing as illustrated.
(III)

(IV)

(V)

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 109
Example

As electron releasing group

As electron withdrawing group

Which behaviour dominates and which is used in a particular

context will be discussed later in Electrophilic Aromatic
Substitution later.
Resonance Effect does NOT depend upon distance unlike
inductive effect.

(b) Applications of Mesomeric Effect

(1) Effect on Acidic Strength of Carboxylic Acids and Phenols

The resonating structure of carboxylic acid leads to charge-
NOTE
separated structure which is less stable than the carboxylate ion in
which charge is delocalized. Therefore, carboxylic acid readily loses Order of acidic strength

proton ( H ) to form a carboxylate ion. RSO3H > RCOOH > PhOH > CH3OH > H2O >
ROH > HCCH > NH3 > CH4

(2)Effect on Reactivity of Carboxylic Acid Derivatives

A typical nucleophilic reaction is represented as :

The stronger is the bond between C and Z, the difficult it is for a

nucleophile to break a bond and therefore, lower reactivity.

Similarly, in phenol, resonance leads to charge separation which

increases the rate of ionization and forms phenoxide ion which is
Reactivity order of carboxylic acid derivatives towards nucleophilic
stabilized by charge delocalization.
acyl substitution is :
Acyl Chloride > Acid Anhydride > Ester > Amide
(3) Effect of ERG/EWG on Acidic/Basic Strength
EWG increases the acidic strength and decreases the basic
strength.
ERG decreases the acidic strength and increases the acidic
strength.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 110
Example 3.4 Hyperconjugation
Arrange the following in the order of decreasing acidic strength :
Hyperconjugation is the ability of the  bond electrons of an 
bond to undergo conjugation with the adjacent  electrons.
It is also known as Baker-Nathan Effect, No-Bond Resonance
and - Effect.

(a) -Carbon and -Hydrogen

We have already discussed the , ,  nomenclature. Let’s take an
example :
Solution :

-Carbon is the carbon attached to a functional group such as

. The hydrogen attached to -carbon is called -hydrogen.
For an  bond to be eligible for hyperconjugation,  C
3
must be sp hybridized.
The order of acidic strength is : II > V > I > III > IV
In the previous example, let’s also discuss the stability of phenoxide (b) Mechanism of Electron Donation in Hyperconjugation
ions corresponding to (II) and (IV).

The hybrid formed by these resonating structures better known

as hyperconjugating structures is :

Now, greater the number of -H, greater the number of

hyperconjugating structures and more is the electron donation of
alkyl group to  bond.
The order of electron-donation of alkyl groups based on
hyperconjugation is :

Methyl > 1° > 2° > 3°

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 111
NOTE 2. Acidic Character of Alkenes
More is the number of -H, more is the bond delocalized. Hyperconjugation weakens the C-H bond in hyperconjugation
This implies that more will be the stability of alkene and less hybrid (partial single bond) and therefore H can be lost easily.
will be the heat of hydrogenation and more is the no-bond
resonance energy.

(c) Applications of Hyperconjugation

1. Stability of Alkenes
3. Stability of Carbocations
More is the number of -hydrogen, more is the number of
hyperconjugating structure and therefore more stability and
greater no bond resonance.

Example

Which alkene is more stable ?

The positive charge on C is delocalized over H to give stability

to the carbocation. More is the number of H, more is the stability
Solution : of carbocations.

I is more stable than II.

Stability of Carbocations

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 112
3.4 Electromeric Effect the lone pair of N is not in conjugation and is readily available for
electron donation. Hence, the order of basic strength is :
Electromeric effect is observed only in the presence of a reagent (I) > (III) > (II)
and is therefore, a temporary effect. When a reagent approaches
a molecule, the multiple bond such as or is polarized Example
by the complete transfer of  electrons. Mark the order of bond lengths in the given molecule.

When the multiple bond is between two unlike atoms, the shift of
electrons takes place towards more electronegative atom.

Solution :
–I, –NO2 are bulky groups and is case of steric inhibition of
Some important points: resonance. Therefore, the –NO2 groups ortho to –I are out of
1. Comparisonof Inductive, Hyperconjugation and Resonance Effects conjugation while the –NO2 group para to –I will be in conjugation
with the benzene ring. Therefore, bonds ‘a’ and ‘b’ will always
Inductive Effect is a s-s interaction and acts through strong sigma have single bond character while ‘c’ has double bond character.
bonds. Therefore : c < a = b
Resonance/Mesomeric Effect is a p-p interaction and acts through
3. Steric Inhibition of PROTONATION (SIP)
weak pi bonds.
Hyperconjugation is a s-p interaction and acts through a strong sigma
and a weak pi bond.
Therefore, the order of importance is :
Resonance > Hyperconjugation > Inductive

2. Steric Inhibition of Resonance (SIR)

When both the ortho positions of a bulky functional group are
occupied by bulky substituents, all the three groups are out of
plane of the benzene ring.
Expected Order : o > p > m > PhNH2
Actual Order* : p > m > PhNH2 > o

4. REACTIVE INTERMEDIATE
Example
4.1 Carbocation
Mark the order of basic strength :
(a) Definition

Carbocation is the intermediate of carbon containing positive

charge. It has six electrons in the valence shell.

(b) Geometry and Hybridization

 2
Solution : Hybridization of C = sp

In (II) and (III), the lone pair of N is in conjugation with the benzene Geometry of C = Trigonal Planar
ring and is not available for donation. (II) is less basic than (III) due
to –I and –M of –NO2 group. It may seem that (I) is least basic due
to presence of 2 –NO2 groups but –NO2 and –N(CH3)2 are all bulky
groups. This is a case of steric inhibition of resonance due to which

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 113
Order of stability :

(c) Classification of Carbocations

This classification will also be used for carbanions and carbon

free radical and will be studied only in this section.
Methyl Carbocation

1° Primary Carbocation Example

2° Secondary Carbocation Rank the stability of carbocations in each case :

3° Tertiary Carbocation

(a)

Solution :
(a)

and +I Effect.
and +I Effect.
(d) Stability of Carbocations
There are three factors contributing to the stability of
carbocations :
(a) Inductive Effect
(b) Hyperconjugation
(c) Resonance

and +I Effect.
Order of stability : III > I > II

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 114
(e) Formation of Carbocations Step-2 : Formation of Carbocation

 Ionization of Carbon-Leaving Group Bond

In this method :
(a) Bond between carbon and leaving group ionizes.
(b) Leaving group accepts the pair of electrons that were shared
in the covalent bond.

Rate of formation of carbocation depends on : Step-3 : Deprotonation

(a) The stability of carbocation formed.
(b) The nature of the leaving group. Weaker the base better the
leaving group. This is because weaker leaving group implies a
stable compound and its formation will therefore be favoured. and +I Effect.
 Addition of Proton to a  bond

Rate of carbocation formation depends on :

(a) Stability of carbocation formed.
(b) Strength of the electrophile. When carbocation deprotonation can lead to more than one product,
all products are formed and the most stable product is the major
(f) Reactions of Carbocations
product.
There are three important reactions of carbocations : 3. Carbocation Rearrangement
(a) Capture a Nucleophile A carbocation can become more stable by rearrangement. Bonding
(b) Loss a proton to form a  bond. electrons of carbocation may shift between adjacent atoms to
form more stable carbocation. There are two kinds of shifts that
(c) Rearrangement
take place in order to gain stability.
1. Capture a Nucleophile (a) Hydride Shift (b) Alkyl Shift

Example
2. Lose a proton to form a  bond

Example

Form the products from the following reaction :

Solution :
Step-1 : Protonation

In the above example, both hydride and methyl shifts are possible
leading to more stable carbocation but only that shift is preferred
which leads to more stable carbocation. In this example, hydride
shift will take place.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 115

Important : The shift takes place in the form of . 4.2 Carbanions

 Cyclic Rearrangement/Ring Expension (a) Definition

Ring expension will take place only when positive charge is on
carbon adjacent to the ring. Carbanion is the intermediate of carbon containing negative charge.
It has eight electrons in the valence shell.
Example

Draw the products of the following reaction :

(b) Geometry and Hybridization

3
Hybridization of : sp
Geometry : Trigonal Pyramidal
Solution :
Carbanion and ammonia are isoelectronic species having same
structure

(c) Stability

ERG will increase the electron density at carbon and will make it
Even though the hydride shift leads to more stable carbocation, unstable. EWG will decrease the electro density at carbon and will
ring expansion is preferred. make it stable.
Order of Stability :

Example

Give the order of stability of :

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 116
Solution : There are three reasons for the easy formation of carbanion from
As s-character increases, electronegativity of C increases and carbonyl compounds
therefore negative charge will become more stable. Therefore, order (a) Resonance - stabilization of carbanion which is the conjugate
of stability is : base of carbonyl compound.
III > II > I (b) Hyperconjugation makes the C-H bond acidic.
(c) –I of increases the acidic strength of C–H bond.

(e) Reactions of Carbanion

The reactions of carbanion are very fast as electropositive carbon

carries negative charge.
(d) Formation of Carbanion
 Grignard Reagent as a Base
There are two methods for the formation of carbanion :
In this reaction it captures acidic hydrogen.
(A) Partial formation via Grignard Reagent
(B) Formation from Carbonyl Compounds
We will discuss these methods in the subsequent section
 Formation via Grignard Reagent

NOTE:

1. Carbanion is never formed as an intermediate that can be isolated

in the case of Grignard Reagent. It directly participates in the
reaction.
2. Dry ether is used in this formation as it is inert to Grignard
reagent. For the formation of Grignard reagent from aryl halides,
we use tetrahedrofuran (THF) as solvent. In (d), the reaction with terminal alkyne also takes place as sp-
hydridized carbon is highly electronegative and therefore H
attached to it is fairly acidic.

 Grignard Reagent as a Nucleophile

 Formation from Carbonyl Compounds Grignard Reagent reacts with carbonyl compounds to form
alcohols. This is a very important method for the synthesis of
alcohols.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 117
Mechanism : electron. It is neutral and has seven electrons in the valence shell.
It is highly reactive as it requires only one electron to complete its
octet and therefore, is short-lived.

(b) Geometry and Hybridization

is never added along with the first step as Grignard Reagent

will react with to give as in previous reaction.

 Aldol Condensation
The hybridization of carbon free radical was proposed after
This reaction is shown by carbonyl compounds containing atleast
experimental verification of structure of different radicals. It was
•
one H in presence of dilute base such as dilute NaOH. 2
proposed that when ERG are placed on C , it has sp hybridization
• 3
and when EWG are placed on C , it has sp hybridization.

Mechanism :

(c) Stability

ERG increase stability while EWG decrease stability.

(d) Formation of Carbon Free Radical

Carbon Free Radicals are formed by homolytic cleavage of bonds.

They are formed :
4.3 Carbon Free Radicals (a) at high temperature in the gas phase
(b) in non-polar solvents
(a) Definition
(c) by ultraviolet light
Carbon Free Radical is the intermediate of carbon having an odd (d) by addition of other radicals

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 118
(e) Reactions of Carbon Free Radical

The most common reactions in which free radical is involved are :

(a) Halogenation of alkanes.
(b) Addition of HBr in the presence of peroxides to alkenes. (Anti-
Markonikov Rule)
There is a side-product that is formed in this reaction.
(c) -Halogenation of alkenes.
Besides these, a number of other side-products such as CH 2 Cl 2 ,
(d) Wurtz Reaction
CHCl3 and CCl4 have also been observed. These get formed
(e) Decarboxylation reaction
since carbon free radical is highly reactive. It randomly reacts with
 Free Radical Halogenation of Alkanes other species that make it stable.
The typical reactions of free radical are chain reaction mechanisms.
5. AROMATICITY
There are three steps in a chain reaction mechanism : initiation,
propagation and termination. It is a property of conjugated cycle in which stability of compound
increased by delocalisation in  orbitals.

Mechanism 5.1 Aromatic compounds (Huckel’s rule)

2
(I) Chain Initiation  Planarity (2-D) [sp carbon]
–
There are two choices :  Conjugated system (de-localisation of e in ring)
 Cyclic
–
 Presence (4n + 2) e in the ring. Where, (n = 0, 1, 2, 3...)
(a)

(b)
(I) (b) will take place as it is energetically feasible.
(II) Chain Propagation
5.2 Anti -Aromatic compounds
(a)
 Cyclic
 Planar
 Conjugated System
–
 4n e should present in the ring where (n = 1, 2, 3...)

(b)

(III) Chain Termination

The various free radicals in the progress of reaction are :
Cl•, CH3•. There are ways in which free radicals from different chains
may combine to terminate the reaction.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 119
5.3 Non-Aromatic compounds Example

 Compound which are neither aromatic nor antiaromatic. n–Butane and isobutane are chain isomers.
CH3–CH2–CH2–CH3

n–butane isobutane

6.1.2 Positional Isomerism

Stability order of compounds: This isomerism arises due to the difference in position of either
Aromatic > non aromatic > Anti-Aromatic substituent or functional group in the same carbon chain.
Example
(i) CH3–CH2–CH=CH2 CH3–CH = CH–CH3
6. ISOMERISM IN ORGANIC CHEMISTRY
But–1–ene But–2–ene
In organic chemistry, a number of organic compounds having (ii) C6H4(NO2)2 exhibits following three positional isomers.
different physical and chemical properties can be represented by
the same molecular formula. The property by virtue of which
organic compounds possessing different physical and chemical
properties and having the same molecular formula is known as
isomerism and the different compounds are known as isomers.
Since the isomers are constituted of the same number of atoms, so
it is clear that the difference in their properties must be due to the
difference in the relative arrangement of the atoms within the
molecules.

6.1 Structural Isomerism 6.1.3 Functional Isomerism

These isomers have same molecular formula but they differ only
If the isomers have the same molecular formula but they differ in in the presence of different functional groups.
the relative arrangement of atoms, it is called structural isomerism.
In structural isomers, the structural formula of the isomers differ
whereas the molecular formula remains same. This type of
isomerism is further divided into various types.

6.1.1 Chain or Nuclear Isomerism

This type of isomerism arises due to the difference in the structure

of carbon chain. The difference may be in the length of the carbon
chain or in the size of the carbon ring.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 120

(i)

(ii) C3H6O exhibits the following functional isomers.

NOTE:
Test for Enols
In those equilibria where the enol content is higher than the
keto form, the solution produces red/green/blue colour with
neutral FeCl3 solution. The appearance of such a colour on
addition of neutral FeCl3 solution is a test for any enol. Phenol
6.1.4 Tautomerism also responds to this test.

This is a special type of functional isomerism where functional Example

isomers exist in equilibrium with each other. Such isomers are called
tautomers.

The necessary condition for this type of isomerism is the presence

of –hydrogen to the carbonyl group (a hydrogen on a carbon Keto enol
adjacent to carbon of functional group).
Example
A very common form of tautomerism is that between a carbonyl
compound containing an hydrogen and its enol form. This type
of isomerism is also known as keto–enol isomerism.

less stable more stable

Example
In general, the keto form is more stable than the enol form but in
some cases the enol form is more stable.

 Cases when the enol form is more stable than the keto form:
(1) Enol form has resonance stabilization by forming a conjugated
3
system and has intra-molecular hydrogen bonding. This cannot show tautomerism as no sp hybridized –carbon
Example is present.

NOTE:
The tautomers are not counted while finding the total number
of isomers for a given molecular formula.

Acetoacetic ester  Diad System : It involves the oscillation of H atom between

two polyvalent atoms, e.g., hydrogen cyanide (I) and
(2) Enol form has aromatic stabilization.
hydrogen isocyanide (II)

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 121
 Triad System : In this one H atom oscillates between three Example
polyvalent atoms.
Keto-enol tautomerism : In this case the polyvalent atoms C4H10O exhibits three metamers.
are one oxygen and two carbon atoms, e.g. aceto acetic
ester, acetyl acetone, benzoyl acetone, acetaldehyde,
aceton, phenol etc.
The form containing keto (oxo) group is called keto while
that having alkene and alcohol group is called an enol form.
 Triad System containing Nitrogen:
Nitrous acid exists in two tautomeric forms :

6.2 Stereo Isomerism

The alkyl derivatives of nitro form and nitric form are called as
nitro alkanes and alkyl nitrites, respectively. In this type of isomerism, the compounds possessing same
Primary and secondary nitroalkanes have labile  -H atom, molecular formula differ in their properties due to the difference in
hence exhibit nitro-acinitro type of tautomerism. the arrangement in space of their atoms or groups in the molecule.

6.2.1 Geometrical Isomerism

It is the type of isomerism in which the compounds possessing

same molecular formula differ in their properties due to the difference
in their geometry that is, due to the difference in the direction of
 Nitroso-isonitroso System : In this system one tautomer attachment of same atoms or groups in their molecule. It is not
exits as nitro while the other tautomer exists as an isonitroso shown by single bonded compounds like (C – C) due to free rotation.
(oxime) form.
It is shown by C = C, C = N, N = N and cycloalkanes.

Conditions for exhibiting Geometrical Isomerism

(a) There must be restricted rotation in the molecule.

 Imine-Enamine System

(b) Groups attached to the doubly bonded carbon or nitrogen must be

different. Lone pair is also considered as a different group.
(i) Cis-Trans Isomerism
6.1.5 Metamerism
Geometrical Isomerism in
It is caused by the attachment of different alkyl groups to a Cis isomers are isomers in which two similar atoms lie on the same
polyvalent atom or group (an atom having more than one valency). side of a double bond in the molecule. On the other hand, trans
A metamer can be obtained by shifting one or more CH2 group isomers feature molecules with two similar atoms placed on
from one side of the polyvalent functional group to the other side. opposite sides of a double bond.
Metamerism is found to occur in amines, ethers, ketones, esters, etc.
Example
Same atoms or groups on same side. So geometrical isomerism is
not possible.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 122
2. In case of isotopes, check the atomic mass of that atom.
Example: H, D
3. Chain Method
Example
Example

For determining priority, use the following method

(ii) Syn-Anti Isomerism
Geometrical isomerism in and
Syn: it is used to indicate that both H and OH are present on the
same side of the double bond. Anti: it is used to indicate that H
and OH are present on the opposite sides of the double bond.

Example

Example 6.2.2 Optical Isomerism

Optical isomers differ in their interaction with the plane polarized

light. The property of rotating the plane polarized light is called
optical activity and the compound that rotates the plane of polarized
light is called optically active compound. The angle by which
plane polarized light is rotated is called the specific rotation of the
compound and is measured by polarimeter.
(iii) E-Z Nomenclature of Geometrical isomers
When C = C contain three or four different groups, it is difficult to  Chirality
assign cis or trans configuration to the geometrical isomers.
Example Chirality means Unsymmetrical. A molecule that is non-
superimposable on its mirror image is chiral. A molecule that is
superimposable on its mirror image is achiral. Chirality is the
necessary and sufficient condition for a compound to show optical
activity.

 Chiral Carbon and Chiral Compound

To deal with such problems, E–Z nomenclature is used.
When a carbon atom is bonded to four different atoms (or groups)
 Cahn - Ingold - Prelog (CIP) Rules
1. Higher atomic number group is assigned higher priority. NOTE
It is not necessary for a chiral compound to contain chiral
carbon.

CWXYZ, it is chiral and is denoted as C*.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 123
 R/S Configuration

The arrangement of atoms that characterizes a particular

stereoisomer is called its configuration.
Example

A compound which is non-superimposable on its mirror image is

called a chiral compound.
Example

Example
 The configuration is assigned for a stereoisomer based on
Cahn-Ingold-Prelog rules by assigning priority to the groups
attached to the chiral carbon.
 The rules that are used for E-Z isomerism are used in the same
way here as well.
 The lowest priority group should be behind the plane while
deciding the configuration.
 If the direction of priorities assigned to groups is clockwise, the
compound has R configuration. If the direction of priorities assigned
to groups is anti-clockwise, the compound has S configuration.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 124
Example Example

 Fischer Projection
Exchange H and NH2 and we get :
It is the two dimensional representation of a tetrahedral carbon.
The method to draw Fischer projection of a molecule has been
illustrated.

Therefore, after the exchange, we get S configuration which means

the given molecule has R configuration.

 Chiral Compounds with Chiral Carbons

Case I : Compounds with only one chiral carbon are always chiral,
i.e. optically active.
 The groups present on the vertical line in Fischer projection
are behind the plane whereas the groups present on the horizontal
line are outside the plane.
NOTE:
R and S configurations are mirror images of each other.
 R/S configuration is assigned in a Fischer projection by
keeping the lowest priority group on the vertical line (behind the Example
plane).

Example

Case II : Chiral compounds containing more than chiral carbon

are chiral only if they do not satisfy any symmetry condition such
 If the lowest priority group is not behind the plane or on the as plane of symmetry or centre of symmetry.
vertical, exchange it with the group that is behind the plane. If any symmetrical condition is satisfied, the compound is achiral.
 When two groups are exchanged, the configuration of that
atom is inversed.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 125
Example Meso compounds are compounds which satisfy any symmetry
condition will be optically inactive due to internal compensation
of rotation.
Diastereomers are stereoisomers which are non-mirror images of
each other.
Racemic Mixture are equimolar mixture of enantiomers. They are
optically inactive due to external compensation of rotation.
Resolution is the process of separation of racemic mixture into
optically active enantiomers.
Example
Example

Example

 Specific Rotation and Nature of Rotation

The d- configuration is relative to the optical activity
experiment whereas R/S configuration is absolute
configuration which is assigned based on priority of groups
Example
according to CIP rules.

Optical activity is the ability to rotate the plane-polarized light.

The optically active isomers are of two types
1. Dextrorotatory : The isomer that rotates the plane-polarized
light to the right (clockwise) is called ‘Dextrorotatory’. It is denoted
as ‘d’ or (+).
2. Laevorotatory : The isomer that rotates the plane-polarized
Example light to the left (anticlockwise) is called ‘Laevorotatory’. It is
denoted as ‘’ or (–).
Optical rotation is measured by polarimeter in terms of specific rotation.
observed
 T 
c
 = specific rotation
observed = observed value of rotation
 = length of solution
 Enantiomers, Diastereomers, Meso Compounds and Racemic
Mixture c = concentration of solution.

Enantiomers are compounds that are non-superimposable mirror

images of each other.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 126
Specific Rotation depends upon : (ii) Conformations of Butane
(a) Nature of solute and solvent.
(b) Wavelength of light during the experiment.
(c) Temperature during the experiment.
(d) Length and concentration of solution.

6.2.3 Conformers

The different spatial arrangements of the atoms that result from

rotation about a single bond are called conformations. A specific
conformation is called a conformer.
When rotation occurs about the carbon-carbon bond of ethane,
two extreme conformations can result-a staggered conformation
and an eclipsed conformation. An infinite number of conformations
between these two extremes are also possible.
The staggered conformation, therefore, is the most stable
conformation of ethane because the C–H bonds are as far away
from each other as possible. The eclipsed conformation is the
least stable conformation because in no other conformation are
the C–H bonds as close to one another.
The extra energy of the eclipsed conformation is called torsional
strain.
(i) Conformations of Ethane Order of stability of conformers of Butane :
Anti > Gauche > Eclipsed > Totally Eclipsed
(iii) Case of Intramolecular Hydrogen Bonding
In case of G-CH2-CH2-OH, where G = -OH, -NH2, -F, -NR2, -NO2, -
COOH, -CHO the Gauche form is more stable than the anti form
due to intramolecular hydrogen bonding.
Example
2-Fluoroethanol

Stability order: Gauche form > Anti form > Partially eclipsed >
Fully eclipsed.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 127

Potential energy of butane as a function of dihedral angle

(iv) Conformation of Cyclohexane

The order of stability of these conformations is

Chair > twist boat > Boat > Half chair

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 128

SUMMARY
Inductive effect : When two unlike atoms form covalent bond, the
electron-pair forming the sigma bond is never shared equally be-
Carbanion:
tween the two atoms but is shifted slightly towards the more
electronegative species.

Resonance: Molecules are generally represented by simple lewis

structures but some molecules can not be represented by just one
Lewis structure. This led to the discovery of resonance. Reso-
nance refers to the delocalization of electrons (generally p-elec-
trons).

Mesomeric Effect: Groups which release or withdraw electrons

by resonance are said to exert M or R effect.
 Electron-Releasing Groups (+R or +M effect)

 Electron-Withdrawing Groups (–R or –M effect)

Carbon Free Radicals:

Hyperconjugation : Hyperconjugation is the ability of the s bond

electrons of an a bond to undergo conjugation with the adjacent
p electrons. It is also known as Baker-Nathan Effect, No-Bond
Resonance and s-p Effect.

Carbocation:

Structural Isomerism: If the isomers have the same molecular

formula but they differ in the relative arrangement of atoms, it is
called structural isomerism. In structural isomers, the structural
formula of the isomers differ whereas the molecular formula remains
same. This type of isomerism is further divided into various types.

Chain or Nuclear Isomerism: This type of isomerism arises due

to the difference in the structure of carbon chain. The difference
may be in the length of the carbon chain or in the size of the
carbon ring.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 129
Positional Isomerism: This isomerism arises due to the difference Elements of Symmetry:
in position of either substituent or functional group in the same
• Plane of Symmetry
carbon chain.
• Axis of Symmetry
Functional Isomerism: These isomers have same molecular • Centre of Symmetry/ Inversion
formula but they differ only in the presence of different functional Chirality: Chirality means unsymmetrical. A molecule that is non-
groups.
superimposable on its mirror image is chiral. A molecule that is
Tautomerism: This is a special type of functional isomerism where superimposable on its mirror image is achiral. Chirality is the
functional isomers exist in equilibrium with each other. Such necessary and sufficient condition for a compound to show optical
isomers are called tautomers. activity.
Metamerism: It is caused by the attachment of different alkyl/ Enantiomers are compounds that are non-superimposable mirror
groups to a polyvalent atom or group (an atom having more than images of each other.
one valency). A metamer can be obtained by shifting one or more
CH2 group from one side of the polyvalent functional group to Meso compounds are compounds which satisfy any symmetry
the other side. Metamerism is found to occur in amines, ethers, condition will be optically inactive due to internal compensation
ketones, esters, etc. of rotation.
Diastereomers are stereoisomers which are non-mirror images of
each other.
Stereo Isomerism: In this type of isomerism, the compounds
possessing same molecular formula differ in their properties due Racemic Mixture are equimolar mixture of enantiomers. They are
to the difference in the arrangement in space of their atoms or optically inactive due to external compensation of rotation.
groups in the molecule. Resolution is the process of separation of racemic mixture into
optically active enantiomers.
Geometrical Isomerism:
• There must be restricted rotation in the molecule. Conformers:The different spatial arrangements of the atoms that
result from rotation about a single bond are called conformations.
• Groups a ttached t o the do ubly bo nd ed carbon or
A specific conformation is called a conformer.
nitrogen must be different. Lone pair is also considered
as a different group. • Order of stability of conformers of Butane :
Anti > Gauche > Eclipsed > Totally Eclipsed
Optical Isomerism: Optical isomers differ in their interaction with
the plane polarized light. The property of rotating the plane
polarized light is called optical activity and the compound that
rotates the plane of polarized light is called optically active
compound.

SCAN CODE
General Organic Chemistry (Revision) & Isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 130

SOLVED EXAMPLES
Example - 1

Which one of the following acids does not exhibit optical

isomerism ? (a) (b)
(a) Lactic acid (b) Tartaric acid
(c) Maleic acid (d) -amino acids
Ans. (c)
(c) (d)
Sol.

Example - 4

The alkene that exhibits geometrical isomerism is

(a) propene (b) 2-methyl propene
(c) 2-butene (c) 2-methyl-2-butene
Ans. (c)
Sol. 2-Butene may exist as cis and trans isomers. The cis-isomer
has the two methyl groups on the same side and the trans-
isomer has the two methyl groups on opposite sides. Due
to restricted rotation around double bond it exhibits
geometrical isomerism.

maleic acid has no chiral centre, so optically inactive. Example - 5

Example - 2 The number of stereoisomers possible for a compound

of the molecular formula
Identify the compound that exhibits tautomerism CH 3  CH  CH  CH(OH)  Me is
(a) 2-butene (b) lactic acid (a) 3 (b) 2
(c) 2-pentanone (d) phenol (c) 4 (d) 6
Ans. (c) Ans. (c)
Sol. Tautomers are isomers of a compound which differ only in Sol. d and l for cis form.
the position of the protons and electrons. The carbon
skeleton of the compound is unchanged. A reaction which d and l for trans form.
involves simple proton transfer in an intramolecular fashion So, a total of 4 isomers are possible.
is called tautomerism. So the correct option is 2-Pentanone.

Example - 3

Out of the following, the alkene that exhibits optical

isomerism is
(a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
(c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
Ans. (c)
Sol. Optical isomerism is shown by the carbon compounds
which possess at least one chiral carbon. In given
structures, (c) has an chiral centre , so it will exhibit optical
isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 131
Example - 6 Example - 9
The absolute configuration of Increasing order of stability among the three main
conformations (Eclipse, Anti, Gauche) of 2–fluoroethanol
is
(a) Eclipse, Gauche, Anti (b) Gauche, Eclipse, Anti
(c) Eclipse, Anti, Gauche (d) Anti, Gauche, Eclipse
Ans. (c)
(a) S, S (b) R, R Sol. Eclipse < Gauche < Anti
(c) R, S (d) S, R In the case of Anti, the two electronegative atoms (F- and
OH-) are oppositely placed and the repulsive forces are
Ans. (b) minimum making the conformation more stable, whereas
Sol. Four different groups attached to the chiral center are in eclipsed the groups are closely placed, thereby showing
maximum steric forces, making the conformation less stable.
arranged in decreasing order of priority. The lowest priority
Gauche- When two electronegative groups at 60o angle
group is placed below the plane of paper. When the
from each other, they make gauche conformation, its
remaining 3 groups in decreasing order of priority are in stability lies in between of eclipse and anti form.
clockwise direction, the configuration is R and when the
direction is counterclockwise, the configuration is S.
Example - 10

Example - 7 Which types of isomerism is shown by 2,3–dichlorobutane ?

(a) Structural (b) Geometric
Which one of the following conformations of cyclohexane
is chiral ? (c) Optical (d) Diastereomerism
(a) Twist boat (b) Rigid Ans. (c)
(c) Chair (d) Boat Sol. As shown in the figure 2,3-dichlorobutane has four optical
isomers.
Ans. (a)
Sol. Twist boat form is chiral as it lacks plane of symmetry

Example - 11

Example - 8 Which of the following compounds is not chiral ?

(a) 1–Chloropentane
Which of the following molecules is expected to rotate the
(b) 2–Chloropentane
plane of polarised light ?
(c) 1–Chloro–2–Methyl Pentane
(d) 3–Chloro–2–Methyl Pentane
(a) (b) Ans. (a)
Sol. 1-chloropentane does not contain any asymmetric carbon
atom, Thus it is not a chiral compound.

(c) (d)

Ans. (a)
Sol. For A :The molecule, which is optically active, has a chiral
centre, is expected to rotate the plane of polarised light.
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 132

Example - 12 Example - 15

Amongst the following compounds, the optically active Among the following four structures I to IV
alkane having lowest molecular mass is
(a) CH3 –– CH2 –– CH2 –– CH3

(b)

(c) (d)
It is true that
(a) all four are chiral compounds
Ans. (c) (b) only I and II are chiral compounds
Sol. (a) There is no stereo center. (c) only III is a chiral compound
(d) only II and IV are chiral compounds
(b) There is no stereo center as there are two same (-CH3)
Ans. (b)
groups on carbon.
Sol. Structure I and II have one chiral carbon each, so I and II
(c) The is one stereo center. All atoms attached to carbon
are chiral compounds and III and IV do not have any chiral
atom are different as you can see in the diagram. So, it is
carbon, so these are achiral.
optically active.
(d) There is no stereo center.
Example - 16

Example - 13 Following types of compounds (as I, II)

Which of the following will have a meso-isomer also ?

(a) 2–Chlorobutane
(b) 2, 3–Dichlorobutane are studied in terms of isomerism in
(c) 2, 3–Dichloropentane (a) chain isomerism (b) position isomerism
(d) 2–Hydroxypropanoic Acid (c) conformers (d) stereoisomerism
Ans. (b) Ans. (d)
Sol. The compound 2, 3-dichlorobutane contains a plane of Sol. These all compounds show stereoisomerism
symmetry. Hence, It is superimposable on its mirror images.
Thus, It has a meso isomer.
Example - 17

Example - 14 Racemic mixture is formed by mixing two

(a) isomeric compounds
For which of the following parameters the structural
isomers C2H5OH and CH3OCH3 would be expected to (b) chiral compounds
have the same values ? (Assume ideal behaviour) (c) meso compounds
(a) Heat of vaporisation (d) enantiomers with chiral carbon
(b) Vapour pressure at the same temperature Ans. (d)
(c) Boiling points Sol. Racemic mixture is formed when two enantiomers of same
compound are mixed in different extent and optically active
(d) Gaseous densities at the same temperature and solution is obtained.
pressure
Ans. (d)
Sol. Since both isomers have the same molecular mass and
hence their densities will be the same at same temperature
and pressure.
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 133

Example - 18 Example - 21
Which one of the following substituents at para-position The compound which is not isomeric with diethyl ether
is most effective in stabilizing the phenoxide is
(a) n-Propyl Methyl Ether (b) Butan–1–ol
(c) 2–Methyl Propan–2–ol (d) Butanone
ions ? Ans. (d)
Sol. Diethyl ether (C2H5OC2H5) will be isomeric will all 4-carbon
(a) –OCH3 (b) –CH2OH saturated alcohols, Butanone (CH 3 CH 2 COCH 3 ) is
unsaturated, has two hydrogen less than the diethyl ether.
(c) –CH3 (d) –COCH3
Ans. (d) Example - 22
Sol. Electron withdrawing group  es stability of phenoxide Which of the following compounds will exhibit cis-trans
ion. So –COCH3 shows, – I and –R effect. (geometrical) isomerism ?
(a) But–2–ene (b) But–2–yne
Example - 19 (c) Butan–2–ol (d) Butanal
Which one of the following compounds will not be soluble Ans. (a)
in sodium bicarbonate ?
(a) 2, 4, 6 – Trinitrophenol
(b) Benzoic acid Sol.
(c) o – Nitrophenol
(d) Benzene sulphonic acid
Ans. (c)
Example - 23
Sol. The acid weaker than H2CO3 is not soluble in NaHCO3. so
it is o-nitrophenol. An isomer of ethanol is
(a) methanol (b) diethyl ether
Example - 20 (c) acetone (d) dimethyl ether
The correct IUPAC name of the following compound: Ans. (d)
Sol. Ethers and alcohols (saturated, acyclic) with same number
of carbons are always isomeric.
CH3 – O – CH3 and CH3 – CH2 – OH are functional isomers.
is
Example - 24
(a) 4 – methyl – 3 – ethylhexane
(b) 3 – ethyl – 4 – methylhexane Which of the following will have least hindered rotation
about carbon-carbon bond ?
(c) 3, 4 – ethylmethylhexane
(a) Ethane (b) Ethylene
(d) 4 – ethyl – 3 – methylhexane
(c) Acetylene (d) Hexachloroethane
Ans. (b)
Ans. (a)
Sol.

Sol.

Ethane has the smallest sized group (H) bonded to

carbons, hence there will be least hindered rotation about
C – C bond.
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 134
Example - 25 Example - 28

The enolic form of acetone contains The optically active tartaric acid is named as D-(+)-tartaric
(a) 9 sigma bonds, 1 pi bond and 2 lone pairs acid because it has a positive
(b) 8 sigma bonds, 2 pi bonds and 2 lone pairs (a) optical rotation and is derived from D–glucose
(c) 10 sigma bonds, 1 pi bond and 1 lone pair (b) pH in organic solvent
(d) 9 sigma bonds, 2 pi bonds and 1 lone pair (c) optical rotation and is derived from D-(+)-glyceraldehyde
Ans. (a) (d) optical rotation when substituted by deuterium
Ans. (c)
Sol. The ‘D’ term in name is derived from D-glyceraldehyde.

Example-29

Sol. 
The carbocation CH3 C HCH3 is less stable than
 
(a) CH 3 CH 2 C H 2 (b) C H3
It has 9  (6 with H, two C – C and one C – O), one  -  
(c)  CH 3 3 C (b) CH3 C H 2
bond and two lone-pairs
Ans. (c)
Example - 26  
Sol.  CH 3
C is more stable than CH3 C HCH3 . Rest all are
3
Isomers which can be interconverted through rotation primary carbocations hence less stable
around a single bond are
(a) conformers (b) diastereomers Example - 30
(c) enantiomers (d) positional isomers
Ans. (a) Which of the following is a temporary effect brought into
play at the requirement of attacking reagent?
Sol. Conformers can be intercoverted through rotation about
C-C bond. (a) Inductive effect (b) Mesomeric effect
(c) Electromeric effect (d) Inductomeric effect
Example - 27 Ans. (c)
Sol. Electromeric effect is a temporary effect brought into play
How many optically active stereoisomers are possible for at the requirement of attacking reagent. Electromeric effect
butane–2, 3–diol ? refers to a molecular polarizbility effect occuring by an
(a) 1 (b) 2 intra-molecular electron displacement.
(c) 3 (d) 4
Ans. (b)
M
CH3 CH3 CH3
Sol. H HO HO H H HO
HO H H HO H HO

CH3 CH3 CH3

I II III

I and II are optically active while III is optically inactive

(meso form).
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 135

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Revision of Degree of Unsaturation , Structural F  COOCH  COCl
9. 3
Isomerism, Electronic Displacement in a Covalent I II III
Bond, Aromaticity and Reaction Intermediates
Which of these groups has –I effect?
1. If unsaturation factor is two, then it means that the struc-
ture should have (a) I (b) II

(a) either two -bonds or two rings or one ring with a (c) III (d) all of these
-bonds.
10. The arrangement of (CH3)3C—, (CH3)2CH—, CH3CH2 —
(b) only two -bonds when attached to benzene or unsaturated group in
(c) only two rings increasing order of inductive effect is
(d) both two -bonds and two rings (a) (CH3)3C — < (CH3)2CH— < CH3CH2—
2. The unsaturation factor of the molecular formula C5H8O is (b) CH3CH2 — < (CH3)2CH — < (CH3)3C —
(a) 1 (b) 2 (c) (CH3)2CH — < (CH3)3C— < CH3CH2 —
(c) 3 (d) 4
(d) (CH3)3C — < CH3CH2 — < (CH3)2CH —
3. The molecular formula of a saturated compound is C2H4Cl2.
The formula permits the existence of two 11. Inductive effect of Cl atom operates in

(a) functional isomers (b) position isomers (a)

(c) optical isomers (d) cis-trans isomers (b)
4. Which of the following is an example of functional
isomerism?
(a) Isopentane and Neopentane (c)
(b) Glucose and Fructose
(d) all of these
(c) Diethyl Ether and 2–Methoxy Propane
(d) –Naphthol and –Naphthol 12.

5. The possible number of alkynes with the formula C5H8 is

Which of these groups has –I effect ?
(a) 2 (b) 3
(a) I (b) II
(c) 4 (d) 5
(c) III (d) all of these
6. Only two isomeric monochloro derivative are possible for
13. Inductive effect of a —CH3 group operates
(a) n–Butane (b) 2, 4–Dimethylpentane
(c) Benzene (c) 2–Methyl propane
7. How many isomers are possible with trisubstituted benzene (a) (b)
with all the three groups same ?
(a) 3 (b) 4
(c) 5 (d) 6
8. The number of isomers for the aromatic compound C7H8O (c) (d) both (b) and (c)
(containing benzene ring) are
(a) 2 (b) 3
(c) 4 (d) 5
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 136
14. Which of the following orbital diagrams represents the case 17.
of hyperconjugation ?

Canonical structures due to hyperconjugation in this

(a) molecule can be written as

(a) (b)
(b)

(c) both (a) and (b)

(d) none of these

15. Hyperconjugation occurs in (c) both (a) and (b) (d) none of these

18. Hyperconjugation occurs in

(a) (b)
(a) CH CH2 (b) CH CH CH3
3 3

(c) CH CH2 CH2 (d) all of these

3
(c) (d) All of these

19.

16. How many hyperconjugable H-atoms does this

Which of the following statements is true about this molecule ?
molecule has ?
(a) C1—C2 and C3—C4 bonds are of same length
(a) 0 (b) 2
(b) C1—C2 bond is shorter than C3—C4 bond
(c) 3 (d) 4
(c) C1—C2 bond is longer than C3—C4 bond

(d) C1—C2 and C2—C3 bonds are of same length

GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 137

20.
22.

The stability order of these canonical structures is

(a) I > II > III (b) III > I > II

(c) I > III > II (d) II > III > I

23. Which of the following is most stable

Among these canonical structures of pyridine, the correct

order of stability is

(a) ( I = V) > (II = IV) > III

(b) (II = IV) > (I = V) > III

(c) (I = V) > III > (II = IV)

(d) III > (II = IV) > (I = V)

(a) I (b) II

(c) III (d) IV

21.
24. Resonance structure of a molecules should have

(a) Identical arrangement of atoms

The most stable canonical structure among these is (b) Nearly the same energy content

(a) I (b) II (c) The same number of paired electrons

(c) III (d) all are equally stable (d) All the above
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 138
25. In the anion, HCOO– the two carbon-oxygen bonds are 29. In which of the following molecules, –NO2 group is not
found to be of equal length. What is the reason for it ? coplanar with phenyl ring ?

(a) Electronic orbits of carbon atom are hybridised

(b) The bond is weaker than the bond

(c) The anion, HCOO– has two resonating structures (a) (b)
(d) The anion is obtained by removal of a proton from
the acid molecule

26. In which of the following molecule the resonance effect is

not present?

(a) (b)
(c) (d)

(c) (d)

30. The hybridization of carbon atoms in C—C single bond of

27. The most unlikely representation of resonance structure H—C C — CH CH2 is :
of p–nitrophenoxide ion is :
(a) sp3 – sp3 (b) sp2 – sp3

(c) sp3 – sp (d) sp – sp2

31. Hybridized carbon atom used in the formation of the

(a) (b) compound CH3 — CH CH — CH2 — CH3 are :

(a) sp and sp3 (b) sp and sp2

(c) only sp (d) sp2 and sp3

32. Which of the following statements is true about hybridization ?

(c) (d) (a) Hybrid orbitals frequently undergo linear overlaps
making sigma bonds.

28. Aniline is weaker base than ethyl amine. This is due to (b) Hybrid orbitals frequently undergo lateral overlaps making
-bonds. In other words, there are several compounds in which
(a) – I effect of NH2 in aniline -bonds are formed using hybrid orbitals.
(b) – R effect of NH2 in aniline (c) Hybrid orbitals are molecular orbitals.
(c) + I effect of NH2 in aniline (d) A hybrid orbital bigger in size makes shorter bond.
(d) + R effect of NH2 in aniline 33.

C1—C2 bond of this molecule is formed by

(a) sp3–sp2 overlap (b) sp2–sp3 overlap

(c) sp–sp2 overlap (d) sp2–sp2 overlap

GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 139
38. Which of the following carbocation is least stable ?
34.

(a) (b) CH CH2

(c) CH CH CH2 (d)

Which of the following orders is correct for the stability of 2
these carbanions ?
(a) I > II > III (b) III > II > I 39. The order of stability of the following carbocations

(c) II > III > I (d) II > I > III

 
CH 2  CH  C H 2 ;CH3  CH 2  C H 2 ;
 I  II 

(a) III > II > I (b) II > III > I

35.
(c) I > II > III (d) III > I > II

40. Which of the following carbocation is most stable?

Which of the following orders is correct for the stability of
these carbanions ?
(a) I > II > III (b) III > II > I (a) (b)

(c) III > I > II (d) II > I > III

36. Arrange the carbanions, (c) (d)

   
 CH3 3 C, C Cl3 ,  CH3 2 C H,C6 H 5 C H 2 in order of 41. Consider the following structures
their decreasing stability  
(I) CH 2  CH (II) CH 3  CH 2
(a)  
(III) CH 2  CH  CH 2 (IV) C 6 H 5  CH  C 6 H 5
(b)
The correct sequence of these carbocations in the
decreasing order of their stability is
(c)
(a) IV, III, II, I (b) I, II, III, IV
(d)
(c) IV, II, III, I (d) I, III, II, IV
37. Which of the carbanion is most stable?
42. Most stable carbocation among the following is

(a) (b) (a) (b)

(c) (d) All are equally stable

(c) (d)
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 140
43. What is the correct order of stability of the given cations: 47. Which among the following free radicals is most stable?

(a) (b)

(c) (d) CH2 CH2

48.

(a) III > II > IV > I (b) I > II > III > IV

(c) III > I > II > IV (d) IV > II > III > I Compare acidic strength:

44. (a) a > b > c (b) b > c > a

(c) b > a > c (d) a > c > b

Which of the following orders is correct for no-bond-

49.
resonance energy of these radicals ?

(a) I > II > III (b) III > II > I

Compare acidic strength:
(c) III > I > II (d) II > III > I
(a) a > c > d > b (b) d > a > c > b
45. The increasing order of stability of the following free
(c) d > c > a > b (d) d > c > b > a
radicals is
   
50. The correct order of increasing acid strength of the
(a)  CH 3  CH   CH 3  C   C6 H 5  CH   C 6 H 5  C compounds
2 3 2 3

    (A) CH3CO2H (B) MeOCH2CO2H

(b)  C6 H 5  C   C 6 H 5  CH   CH 3  C   CH 3  CH
3 2 3 2

   
(c)  C6 H 5  CH   C6 H 5  C   CH 3  C   CH 3  CH (C) CF3CO2H (D) is
2 3 3 2

   
(d)  CH 3  CH   CH 3  C   C6 H 5  C   C 6 H 5  CH
2 3 3 2
(a) B < D < A < C (b) D < A < C < B

(c) D < A < B < C (d) A < D < C < B

46.

Which of the following orders is correct for no-bond-

resonance energy of these radicals ?

(a) I > II > III (b) III > II > I

(c) I > III > II (d) II > I > III

GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 141
51. Ease of ionization to produce carbocation and bromide 56. Which of the following is aromatic?

ion under the treatment of Ag will be maximum in which
of the following compounds?
(a) (b)

(a) (b)
Br Br (c) (d)
O
57. Which of the following is Anti-aromatic?

(c) (d) (a) (b)

Br Br

52. Among the following alkenes (c) (d) All of these

(I) 1–Butene (II) cis–2–Butene 58. Which of the structures below would be aromatic?
(III) trans–2–Butene
the decreasing order of stability is
(i) (ii)
(a) III > I > II (b) I > II > III

(c) II > I > III (d) III > II > I

53. Which of the following is aromatic compound? (iii) (iv)

(a) i and iv (b) i, iii and iv

(a) (b) (c) iii and iv (d) ii
Geometrical Isomerism
59. Geometrical isomerism will be exhibited by
(c) (d) (a) Pent–1–ene
(b) 3–Methylbut–1–ene
54. Which of the following is Aromatic?
(c) Pent–2–ene
(d) All of these compounds
(a) (b)
60. Which of the following compounds can show geometrical
isomerism ?
(c) (d) All of these (a) Vinyl chloride (b) 1, 1–Dichloroethene
(c) 1, 2–Dichloroethene (d) Trichloroethene
55. Which of the following is non-Aromatic ?
61. Which of the following compounds does not exhibit
geometrical isomerism ?
(a) (b)
(a) 1, 1–Dichlorobut–2–ene
(b) 1, 2–Dichlorobut–2–ene
(c) (d) All of these
(c) 1, 1–Dichlorobut–1–ene
(d) 2, 3–Dichlorobut–2–ene
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 142
62. Of the following compounds, which will have zero dipole 69. The most stable conformation of 1,2-diphenylethane is
moment ?
(a) 1, 1-Dichloroethylene
(b) cis-1, 2-Dichloroethylene (a) (b)
(c) trans-1, 2-Dichloroethylene
(d) None of these compounds
63. The number of isomers-1 of dibromo derivative of an alkene
(molar mass 186 g mol ) is
(a) two (b) three (c) (d)
(c) four (d) six
64. Maleic acid and fumaric acid are
(a) Position isomers 70. Which of the following is a conformer of isobutane?

(b) Geometrical isomers

(c) Enantiomers
(a) (b)
(d) Functional isomers
65. Which of the following compounds can exhibit geometrical
isomerism ?
(a) Hex–1–ene (b) 2–Methylpent–2–ene
(c) 3–Methylpent–1–ene (d) Hex–2–ene
66. Each of the following compounds show geometrical (c) (d)
isomerism except
(a) But–2–en–1, 4–dioic acid
71. The Newman projection below represents
(b) But–2–yn–1, 4–dioic acid
(c) But–2–ene
(d) 3–Chlorohex–2–ene
Conformational Isomerism and Tautomerism
67. The most stable conformation of ethylene glycol is
(a) anti (b) gauche
(a) A staggered form of 2-methyl propane
(c) fully eclipsed (d) partially eclipsed
(b) A gauche form of butane
68. Which conformation of the alkane has the highest potential
energy? (c) An eclipsed form of 2-methyl propane
(a) Eclipsed (d) A most stable conformation of 2-methyl butane
(b) Skew 72. The Baeyer’s angle strain is expected to be maximum in
(c) Staggered (a) cyclopentane (b) cyclodecane
(d) All will have equal potential energy (c) cyclooctane (d) cyclohexane
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 143
O 76. Which will show E and Z isomerism ?
(a) (b)
73. I ` II (c) (d)
77. What is the IUPAC name of the following compound ?

OH

(a) (Z)-2-Methylpent-2-enoic acid

III (b) (E)-2-Methylpent-2-enoic acid
(c) (Z)-2-Methylpent-2-ene carboxylic acid
Stability order among these tautomers is
(d) (E)-2-Methylpent-2-ene carboxylic acid
(a) I > II > III (b) III > II > I
78. The correct configuration name of
(c) II > I > III (d) II > III > I
74. The order of stability of the following tautomeric
compounds is

(a) (2E, 5E) (b) (2Z, 5Z)

(c) (2E, 5Z) (d) (2Z, 5E)

H3C Cl
79. C C
H Br
This compound can be named as
(a) III > II > I (b) II > I > III
(a) only cis-1-bromo-1-chloro-propene
(c) II > III > II (d) I > II > III
(b) only trans-1-bromo-1-chloro-propene
E & Z and Syn & Anti Isomerism
(c) trans-1-bromo-1-chloro-propene as well (z)-1-bromo-
75. Which is a pair of geometrial isomers ? 1chloro-propene
(d) only (E)-1-bromo-1-chloropropene
80. What is the configuration of the given molecule ?

(a) (1E,3Z) (b) (1E,3E)

(c) (1Z,3Z) (d) (1Z,3E)
(a) I and II (b) I and III
(c) II and IV (d) III and IV
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 144
81. What is the IUPAC name of the following compound ? 86. Which of the following compounds has asymmetric
centre?

Br
O
(a) (b)

(a) (1Z,3E)-4-Bromo-1-chloro-4-fluoro-1-iodobuta-1,3-diene
Br
(b) (1E,3Z)-4-Bromo-1-chloro-4-fluoro-1-iodobuta-1,3-diene
(c) (d) both (b) and (c)
(c) (1Z,3E)-1-Bromo-4-chloro-1-fluoro-4-iodobuta-1,3-diene
Br
(d) (1E,3Z)-1-Bromo-4-chloro-1-fluoro-4-iodobuta-1,3-diene
87. The compound has:
82. Which of the following compound will not exhibit
geometrical isomerism ?
(a)
(b)
(c)

(d) (a) plane of symmetry (b) axis of symmetry

(c) center of symmetry (d) no symmetry

Optical Active Compounds 88. Rotation of polarised light can be measured by

83. Which of following have asymmetric carbon atom ? (a) Monometer (b) Galvanometer

(a) CH2Cl–CH2Br (b) CH3CHCl2 (c) Polarimeter (d) Viscometer

(c) CH3CH2Cl (d) CH2Br–CHOH–CH3 89. Which of the following will not show optical activity ?

(a)
84. Number of chiral carbon atom in

(a) 2 (b) 4
(c) 3 (d) 1
85. A stereo-center is (b)

(a) An atom in which an interchange of any two group will

result in a new stereoisomer
(c) CH3CH2CH2CH2OH
(b) A chiral carbon atom
(d) CH3 — CH2 — CH — CH3
(c) Both of these |
OH
(d) none of these
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 145
90. An organic compound C4H8O, is found to be optically 95. Consider the following organic compound.
active. Which of the following could it be ?
(a) CH3 –– CH2 –– CH2 –– CHO
(b) CH3 –– CO –– CH2 –– CH3 To make it a chiral compound, the attack should be on carbon
(a) 1 (b) 3
(c) CH 2  CH  CH  OH   CH3
(c) 4 (d) 7
(d) (CH3)2CH –– CHO
96. Which of the following compounds has asymmetric
91. Addition of HCl according to markownikoff’s rule centre?
The conversion of dextro- or laevo- form into racemic mixture
is called O O O

(a) Resolution (b) Racemisation (a) (b)

O
(c) Dehydration (d) Revolution
OH OH
92. The process of separation of racemic mixture into d and 
enantiomers is called
(c) Br (d)
(a) resolution (b) racemisation
(c) filtration (d) distillation Br
93. How many asymmetric carbon atoms are present in : 97. Which of the following structures is chiral?

(i) 1, 2–dimethyl cyclohexane

(ii) 3–methyl cyclopentene
(a) (b)
(iii) 3–methyl cyclohexene
(a) two, one, one (b) one, one, one
(c) two, none, two (d) two, none, one
94. Which of the following compounds has asymmetric centre ? (c) (d)
(a) CH2 CH CH CH CH2
98. Consider following structures and write correct statements
Br

(b)
(1) (2)
Br

(c)

(3) (4)
Br
O

where R1 R2 R3 R4

(d)
(a) Only 4 shows optical isomerism

Br
(b) 1 and 2 show optical isomerism
(c) 1, 2 and 4 show optical isomerism
(d) All show optical isomerism
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 146
99. Which of the following compound may exhibit optical activity ? 103. Which of the following shows optical isomerism ?
(a) cis–1, 2–Dimethyl cyclohexane
(a) (b) (CH3)2C(OH)CN (b) trans–1, 3–Dimethyl cyclohexane
(c) trans–1, 4–Dimethyl cyclohexane
(d) All of the above
(c) (d) 104. Which of the following is optically active ?

100. Optical rotation produced by is 36°,

(a) (b)

then that produced by is

(c) (d) All of these

(a) – 36° (b) 0°

105. Which of the following is optically active ?
(c) + 36° (d) unpredictable
101. From the structure of the three stereoisomers of tartaric
acid, which statement should be true ?
(a) (b)

(c) (d)
(a) 1 is (+), 2 is (–), and 3 is optically inactive
106. Which one of the following alkene, when reacted with HCl
(b) 1 is (–), 2 is (+), and 3 is optically inactive produces racemic mixture ?
(c) 1 is (+), 2 is (–), and 3 is meso
(d) 3 is optically inactive, but nothing can be said about 1 (a) (b)
and 2
102. The following compound can exhibit : (c) (d)
107. When an optically active compound is placed in a 10 dm
tube, is present 20 g in a 200 mL solution rotates the plane
polarized light by 30o. Calculate the angle of rotation and
specific angle of rotation if above solution is diluted to 1 L.
(a) 16o and 36o (b) 6o and 30o
(a) geometrical isomerism
(c) 3o and 30o (d) 6o and 36o
(b) geometrical and optical isomerism
108. An enantiomerically pure acid is treated with racemic mixture
(c) optical isomerism of an alcohol having one chiral carbon. The ester formed
will be
(d) tautomerism
(a) Optically active mixture
(b) Pure enantiomer
(c) Meso compound
(d) Racemic mixture
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 147
Absolute and Relative Nomenclature 113. Determine the absolute configurations of the chiral centres
in the following compound.
109. Rank of the following groups in decreasing order of R, S
precedence.
– CH(CH3)2 – CH2CH2Br – CH2Br – C(CH3)3
1 2 3 4
(a) 3 2 4 1
(b) 1 4 2 3 (a) a = R; b = S (b) a = R; b = R

(c) 3 4 1 2 (c) a = S; b = S (d) a = S; b = R

(d) 3 4 2 1 114. The structure of (S)-2-fluorobutane is best represented by:

110. The absolute configurations of the two centres in the fol-

lowing molecules are:
(a) (b)
1
COOH
2
H Br
3
H CN
(c) (d)
OH
(a) 2(R), 3(S) (b) 2(R), 3(R)
(c) 2(S), 3(S) (d) 2(S), 3(R)
Relationship Between Optical Isomers
111. The configuration at C-2 and C-3 of the compound given:
115. A pair of optically active compounds which are not the
CH3 mirror images are called
H Cl (a) Mesomers (b) Anomers

Cl H (c) Epimers (d) Diastereomers

C2H5 116. Meso form of tartaric acid is :

(a) 2R, 3S (b) 2S, 3R (a) Dextorotatory

(c) 2S, 3S (d) 2R, 3R (b) Laevorotarory

112. Correct configuration of the following molecule is: (c) Neither Laevo nor dextro rotatory due to internal
compensation
CH3 (d) A mixture of equal quantities of dextro and levo rotatory
H OH forms

OH 117. Which of the following statements is true about these two

CH3
structures ?
H
(a) 1S, 2S (b) 1S, 2R
(c) 1R, 2S (d) 1R, 2R

(a) I and II are a pair of enantiomers

(b) I and II are a pair of diastereomers
(c) I and II are a pair of conformers
(d) I and II are a pair of structural isomers
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 148
118. The correct statement about the compound A, B and C

121. are _______ isomer..

(a) Position (b) Optical

(a) A and B are identical
(c) Geometrical (d) Diastereomers
(b) A and B are diastereomers
Number of Optical Isomers
(c) A and C are enantiomers
122. The number of enantiomers of the compound
(d) A and B are enantiomers CH3CHBrCHBrCOOH is
(a) 1 (b) 2
(c) 3 (d) 4
119.
123. CH3 CH CH CH2
I II
OH
How many geometrical and optical isomers are possible in
this compound ?
(a) 0, 2 (b) 0, 3

III IV (c) 2, 0 (d) 2, 2

Which of the following statements is true about these mol- 124. CH3 CH CH CH2 CH3
ecules?
(a) I is a mesomer OH OH
How many optical isomers are possible in this compound ?
(b) I and II are identical
(a) 2 (b) 3
(c) III and IV are a pair of enantiomers
(c) 4 (d) 5
(d) all of these
125. CH3 CH CH CH3
120. The two structures (I) and (II) represented below are
OH OH
How many optical isomers are possible in this compound ?
(a) 2 (b) 3
(c) 4 (d) 5
(a) enantiomers 126. Number of stereoisomers of the compound, 2-chloro-4-
(b) diastereomers methylhex-2-ene is

(c) two representations of the same molecule (a) 2 (b) 4

(d) functional isomers (c) 8 (d) 16

GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 149
127. The compound, whose stereochemical formula is written 129. Number of Stereoisomers for CHO – CHOH – CHOH –
below, exhibits x geometrical isomers and y optical isomers CH2OH is
(a) 2 (b) 4
(c) 6 (d) 8

130. The number of optical active isomers possible for

The values of x and y are :
is
(a) 4 and 4 (b) 2 and 2
(a) 2 (b) 3
(c) 2 and 4 (d) 4 and 2
(c) 6 (d) 8
128. The number of stereoisomers for pent-3-en-2-ol is
(a) 2 (b) 3
(c) 4 (d) 5
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 150

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

1. The optically inactive compound from the following is 6. Which of the following compounds will be suitable for
(2015) Kjeldahl's method for nitrogen estimation ? (2017)
(a) 2-chloropropanal (b) 2-chloropentane
(c) 2-chlorobutane (d) 2-chloro-2-methylbutane
2. The number of structural isomers for C6H14 is : (a) (b)
Online 2015 SET (1)
(a) 4 (b) 3
(c) 6 (d) 5
3. Which of the following statements is not true about (c) (d)
partition chromatography ? (2016)
(a) Mobile phase can be a gas.
7. The number of geometrical isomers in the following
(b) Separation depends upon equilibration of solute compound
between a mobile and a stationary phase.
CH3—CH=CH—CH=CH—C2H5 is
(c) Paper chromatography is an example of partition Online 2017 SET (1)
chromatography. (a) 4 (b) 3
(d) Stationary phase is a finally divided solid absorbent. (c) 2 (d) 5
4. The configuration of the chiral centre and the geometry of 8. The IUPAC name of the following compound is :
the double bond in the following molecule can be described
by Online 2016 SET (1)

Online 2017 SET (1)

(a) 1, 1-Dimethyl-2-ethylcyclohexane
(b) 2-Ethyl-1, 1-dimethylcyclohexane
(c) 1-Ethyl-2, 2-dimethylcyclohexane
(a) R and E (b) S and E
(d) 2, 2-Dimethyl-1-ethylcyclohexane
(c) R and Z (d) S and Z
9. Which of the following compounds is most reactive to an
5. The “N” which does not contribute to the basicity for the aqueous solution of sodium carbonate ?
compound is : Online 2016 SET (2)
Online 2017 SET (2)

(a) (b)

(c) (d)
(a) N 7 (b) N 9
(c) N 1 (d) N 3
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 151
10. In the following structure, the double bonds are marked 13. The IUPAC name of the following compound is :
as I, II, III and IV Online 2018 SET (1)

(a) 4-methyl-3-ethylhex-4-ene
(b) 3-ethyl-4-methylhex-4-ene
(c) 4-ethyl-3-methylhex-2-ene
Geometrical isomerism is not possible at site (s) : (d) 4, 4-diethyl-3-methylbut-2-ene
Online 2017 SET (2)
14. Two compounds I and II are eluted by column
(a) III (b) I chromatography (adsorption of I > II). Which one of
following is a correct statement ? Online 2018 SET (2)
(c) I and III (d) III and IV
(a) I moves faster and has higher Rf value than II
11. Which of the following compounds will show highest
dipole moment Online 2017 SET (2) (b) II moves faster and has higher Rf value than I

(c) I moves slower and has higher Rf value than II

(d) II moves slower and has higher Rf value than I

15. The increasing order of the acidity of the following
carboxylic acids is : Online 2019 SET (1)

(a) I (b) II
(c) III (d) IV
12. Among the following compounds, the increasing order of
their basic strength is : Online 2017 SET (2)

(a) I < III < II < IV (b) IV < II < III < I
(c) II < IV < III < I (d) III < II < IV < I
16. In the following compounds, the decreasing order of basic
strength will be : Online 2019 SET (3)
(a) C2H5NH2 > NH3 > (C2H5)2 NH
(b) NH3 > C2H5NH2 > (C2H5)2 NH
(a) (I) < (II) < (IV) < (III) (b) (I) < (II) < (III) < (IV)
(c) (C2H5)2 NH > C2H5NH2 > NH3
(c) (II) < (I) < (IV) < (III) (d) (II) < (I) < (III) < (IV)
(d) (C2H5)2 NH > NH3 > C2H5NH2
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 152
17. Which of these factors does not govern the stability of a 21. The correct order of acid character of the following
conformation in acyclic compounds ? compounds is: (2021-02-25/Shift-2)
(2019-04-10/Shift-2)
(a) Torsional strain
(b) Angle strain
(c) Steric interactions
(d) Electrostatic forces of interaction
18. In the following skew conformation of ethane, H'–C–C–H"
dihedral angle is : (2019-04-12/Shift-2)
(a) IV > III > II > I (b) II > III > IV > I
(c) III > II > I > IV (d) I > II > III > IV
1 2 3 4
22. In C H 2  C  C H  C H 3 molecule, the hybridization
of carbon 1, 2, 3 and 4 respectively, are:
(2021-02-26/Shift-2)
(A) 58º (B) 120º
(a) sp2, sp, sp2, sp3
(C) 149º (D) 151º
(b) sp3, sp, sp3, sp3
19. Among the following compounds, geometrical
(c) sp2, sp3, sp2, sp3
isomerism is exhibited by :
(d) sp2, sp2, sp2, sp3
(2020-09-05/Shift-2)
23. Among the following, the aromatic compounds are:
(2021-03-16/Shift-1)
(a) (b)
(A) (B)

(C) (D)
(c) (d)
Choose the correct answer from the following options

20 Which one of the following compounds is non- (a) (A) and (B) only (b) (B) and (C) only
aromatic? (2021-02-24/Shift-2) (c) (A), (B) and (C) only (d) (B), (C) and (D) only

(a) (b)

(c) (d)
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 153
24. Assertion (A): Enol form of acetone [CH3COCH3] exists 28. Which of the following molecules does not show
in < 0.1% quantity. However, the enol form of acetyl stereoisomerism? (2021-07-22/Shift-2)
acetone [CH3COCH2OCCH3] exists in approximately
15% quantity. (a) 3, 4-Dimethylhex-3-ene
Reason (R): Enol form of acetyl acetone is stabilized by (b) 3-Methylhex-1-ene
intramolecular hydrogen bonding, which is not
(c) 3-Ethylhex-3-ene
possible in enol form of acetone.
Choose the correct statement: (2021-03-16/Shift-1) (d) 4-Methylhex-1-ene
29. Which one among the following resonating structures
(a) Both A and R are true but R is not the correct
explanation of A is not correct? (2021-07-25/Shift-1)

(b) Both A and R are true and R is the correct

explanation of A
(c) A is true but R is false (a)
(d) A is false but R is true
25. Compound with molecular formula C3H6O can show :
(2021-03-18/Shift-1)
(a) Both positional isomerism and metamerism (b)

(b) Metamerism
(c) Functional group isomerism
(d) Positional isomerism
(c)
26. In the following molecule,

(d)
Hybridisation of Carbon a, b and c respectively are:
(2021-03-18/Shift-2)
30. Which among the following is the strongest acid?
(a) sp3, sp, sp (b) sp3, sp, sp2
(c) sp3, sp2, sp (d) sp3, sp2, sp2 (2021-07-25/Shift-2)

27. Which of the following compounds does not exhibit

resonance? (2021-07-22/Shift-2)
(a) CH3CH2CH2CH3 (b)

(a) CH3CH2OCH = CH2 (b)

(c) (d)
(c) CH3CH2CH2CONH2 (d) CH3CH2CH = CHCH2NH2
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 154
31. Given below are two statements: 35. Choose the correct name for compound given below:
Statement I: Hyperconjugation is a permanent effect.
Statement II: Hyperconjugation in ethyl cation

(CH 3  C H 2 ) involves the overlapping of Csp2  H1s
bond with empty 2p orbital of other carbon.
(2021-08-31/Shift-1)
Choose the correct option (2021-07-27/Shift-2)
(a) Both statement I and statement II are false (a) (4E)-5-Bromo-hex-4-en-2-yne
(b) Statement I is incorrect, but statement II is true (b) (2E)-2-Bromo-hex-4-yn-2-ene
(c) Statement I is correct, but statement II is false (c) (2E)-2-Bromo-hex-2-en-4-yne
(d) Both Statement I and statement II are true (d) (4E)-5-Bromo-hex-2-en-4-yne
36. The total number of C–C sigma bond/s in mesityl
oxide (C6H10O) is ............... (Round off to the Nearest
Integer) (2021-03-17/Shift-2)
32. 37. The number of acyclic structural isomers (including
geometrical isomers) for pentene are ______
(2021-07-22/Shift-2)
The correct order of stability of given carbocation is: 38. The number of sigma bonds in (2021-07-25/Shift-1)
(2021-07-27/Shift-1)
H 3 C  C  CH  C  C  H is _________.
(a) A > C > B > D (b) D > B > C > A |
H
(c) D > B > A > C (d) C > A > D > B
39. The dihedral angle in staggered form of Newman
33. Which one of the following compounds is non- projection of 1, 1, 1-Trichloro ethane is ......... degree.
aromatic? (2021-08-26/Shift-2) (Round off to the nearest integer) (2021-07-27/Shift-2)

40. Which of the following is an aromatic compound?

(2021-03-17/Shift-1)

(a) (b)
(a) (b)

(c) (d) (c) (d)

34. The number of stereoisomers possible for

1, 2-dimethyl cyclopropane is:
(2021-08-26/Shift-2)

(a) One (b) Four

(c) Two (d) Three
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 155
43. Arrange the following conformational isomers of
n-butane in order of their increasing potential energy:

41.

Among the given species the resonance stabilised

carbocations are: (2021-07-20/Shift-1)
(2021-08-31/Shift-2)
(a) (C) and (D) only (b) (A), (B) and (D) only
(a) II < III < IV < I (b) I < IV < III < II
(c) (A) and (B) only (d) (A), (B) and (C) only
42. Which one of the following pairs of isomers is an (c) II < IV < III < I (d) I < III < IV < II
example of metamerism? (2021-07-20/Shift-2) 44. Which one of the following compounds is aromatic in
nature? (2021-09-01/Shift-2)

(a)
(a) (b)

(b)
(c) (d)

45. Mesityl oxide is a common name of :

(c)
(2021-03-17/Shift-1)
(a) 4-Methyl pent-3-en-2-one

(d) (b) 2,4-Dimethyl pentan-3-one

(c) 3-Methyl cyclohexane carbaldehyde
(d) 2-Methyl cyclohexanone
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 156

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only one correct option] 5. Among the following alkenes
1. Which one of the following compound will show (I) 1–Butene (II) cis–2–Butene
geometrical isomerism ? (III) trans–2–Butene
the decreasing order of stability is
(a) (b) (a) III > I > II (b) I > II > III
(c) II > I > III (d) III > II > I
6. Write the correct order of acidity:
(c) (d)

2. Which of the following can not show optical activity ?

(P) (Q)

(a)

(R) (S)
(a) P > Q >R > S (b) Q > P > R > S
(c) Q > R > S > P (d) S > R > Q > P
(b)
7. Number of isomers which can be obtained theoretically on
monochlorination of 2–methylbutane is
(a) 2 (b) 3
(c)
(c) 4 (d) 5
(d) CH3CH2CH2CH2CHO 8. How many structural (including stereoisomers) isomers
3. Isomers which can be interconverted through rotation could be obtained by replacing one hydrogen of propene
around a single bond are with chlorine ?

(a) conformers (b) diastereomers (a) 2 (b) 3

(c) enantiomers (d) positional isomers (c) 4 (d) 5

4. The degree of unsaturation or index of hydrogen deficiency 9. The compound which is not isomeric with diethyl ether
in the following is: is

(i) C6H14 (ii) C4H6 (a) n-Propyl Methyl Ether

(iii) C6H6 (b) Butan–1–ol

(a) 0, 2, 4 (b) 1, 0, 2 (c) 2–Methyl Propan–2–ol

(c) 4, 1, 0 (d) 2, 0, 4 (d) Butanone

10. An isomer of ethanol is
(a) methanol (b) diethyl ether
(c) acetone (d) dimethyl ether
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 157
11. How many possible carboxylic acids and esters are for a 16. – CHO – COOH – CN – NO2
compound with molecular formula C4H8O2 ? I II III IV
(a) four (b) six Among these groups, which of the following orders is the
correct priority order in accordance with sequence rule?
(c) five (d) eight
(a) IV > III > II > I (b) IV > II > I > III
12. The molecular formula of diphenyl methane
(c) II > I > III > IV (d) III > IV > II > I

is C13H12. 17. Which of the following compounds will exhibit cis-trans

(geometrical) isomerism?
(a) But–2–ene (b) But–2–yne
How many structural isomers are possible when one of the
hydrogen is replaced by a chlorine atom ? (c) Butan–2–ol (d) Butanal
(a) 4 (b) 6 18. Which of the following swithing or rotating Fischer struc-
tures changes its absolute configuration?
(c) 7 (d) 8
(a) An even number of switches
13. The enolic form of acetone contains
(b) An odd number of switches
(a) 9 sigma bonds, 1 pi bond and 2 lone pairs
(c) Rotating the Fischer projection by 180o in the plane of
(b) 8 sigma bonds, 2 pi bonds and 2 lone pairs the paper
(c) 10 sigma bonds, 1 pi bond and 1 lone pair (d) Exchange ligands across the horizontal as well as those
(d) 9 sigma bonds, 2 pi bonds and 1 lone pair across the vertical bond

14. Which one of the following compounds cannot show 19. Which of the following operations on the Fischer formula
tautomerism ?
does not changes its absolute configuration?

(a) (b) (a) Exchanging groups across the horizontal bond

(b) Exchanging groups across the vertical bond
(c) Exchanging groups across the horizontal bond and also
across the vertical bond
(d) Exchanging a vertical and horizontal group
(c) (d)
20. Which of the following combinations amongst the four
Fischer projections represents the same absolute configu-
15. Which can not exhibit tautomerism here rations?

(a) (b)
I II

(c) (d) III IV

(a) II and III (b) I and IV
(c) II and IV (d) III and IV
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 158
21. Which of the Fischer projection formula correspond to the
following stereostructure? 25.

This compound can be named as

(a) only trans-3-methyl-2-pentene
(b) only 3-methyl-(2Z)-pentene
(a) (b) (c) trans-3-methyl-2-pentene as well as 3-methyl-(2Z)-
pentene
(d) trans-3-methyl-2-pentene as well as 3-methyl-(2E)-
pentene
26. The most stable conformer of meso-1,2-dibromo-1,2-
(c) (d) dichloro ethane is

22. How many open chain structural isomers of compound with

molecular formula C6H12 show geometrical isomerism ?
(a) (b)
(a) 2 (b) 3
(c) 4 (d) 5

23.
(c) (d)
How many geometrical isomers of this bromonium ion are
possible?
(a) 0 (b) 2
27. Which of the following molecules have (2R, 3-Z) configu-
(c) 3 (d) 4 ration?

(a)
24.

This compound can be named as (b)

(a) 3-chloro-6-methyl-(3E, 5Z)-octadiene
(b) 3-chloro-6-methyl-(3Z, 5E)-octadiene
(c) 3-chloro-6-methyl-(3Z, 5Z)-octadiene
(c)
(d) 3-chloro-6-methyl-(3E, 5E)-octadiene

(d)
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 159
28. Count the number of stereocentres in the molecule below 34. Which of the following will have least hindered rotation
about carbon-carbon bond ?
(a) Ethane (b) Ethylene
(c) Acetylene (d) Hexachloroethane
35. Number of stereoisomers of the compound 2–chloro–4–
methylhex–2–ene is
(a) 2 (b) 4
(a) three (b) five
(c) 8 (d) 16
(c) six (d) seven
36. Which of the following on standing in dilute, aqueous ba-
29. How many optically active stereoisomers are possible for sic solution will undergoes racemization?
butane–2, 3–diol?
(a) Ph–CHBr–CH2–CHO
(a) 1 (b) 2
(b) PhCHBr–CHCl–CHO
(c) 3 (d) 4
(c) Ph–CH2–CHBr–CHO
30. The optically active tartaric acid is named as D-(+)-tartaric
acid because it has a positive (d) Ph–CHClCHBr–CHO
(a) optical rotation and is derived from D–glucose 37. The Fischer projection that represent enantiomer of the
given sawhorse projection is
(b) pH in organic solvent
(c) optical rotation and is derived from D-(+)-glyceraldehyde
(d) optical rotation when substituted by deuterium
31. Which of the following compounds is optically active?
(a) 1-bromobutane
(b) 2-bromobutane
(a) (b)
(c) 1-bromo-2-methylpropane
(d) 2-bromo-2-methylpropane
32 Which of the following amines have a stereogenic centre?

(c) (d)
(a) (b)

38. Which of the following are resolvable?

(c) (d)

(a) a, b, c (b) c, d, e
(a) (b)
(c) a, c, d (d) b, c, d
33. Following pair of molecules are related as

and

(a) enantiomers (b) diastereomers (c) (d)

(c) identical (d) constitutional isomers

GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 160
Objective Questions II 44. Which of the following compound can exhibit geometrical
isomerism ?
[One or more than one correct option]
39. Only two isomeric monochloro derivatives are possible for
(a) n–Butane (b) 2, 4–Dimethylpentane (a)
(c) Benzene (d) 2–Methylpropane
40. HCN and HNC are...... isomers :
(a) Functional (b) Tautomers (b)
(c) Chain (d) Position
41. Which can exhibit tautomerism here
(c)

(a) (b)
(d)
45. Which of these compound can exhibit geometrical isomerism ?

(a) (b)

(c) (d)

42. Keto–enol tautomerism is observed in (c) (d)

(a) 46. Which of the following can show geometrical isomerism ?

(a) (b)
(b)

(c) (c) (d)

47. Which of the following do not show geometrical

(d)
isomerism?
43. CH3CH2NO2 will show ........... isomerism
(a) Position (b) Functional (a)

(c) Tautomerism (d) Geometrical

(b)

(c)

(d)
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 161
53. Which of the following molecules is identical with that
48. Which is/are correct statements about represented by
P and Q ?
(a) P is cis and Q is trans
(b) P is Z and Q is E
(c) P is R and Q is S
(d) P and Q are same structure
49. Which of the following represent a pair enantiomers ?
(a)

(a) (b)

(b)
(c) (d)

50. An organic molecule necessarily shows optical acitvity if it

(a) contains asymmetric carbon atoms
(b) is non-superimposable on its mirror image (c)
(c) is superimposed on its mirror image.
(d) is chiral
51. Which of the following have asymmetric carbon atom?

(d)
(a) (b)

54. Which of the following compounds can show geometrical

isomerism as well as tautomerism here ?
(c) (d)

(a)
52. Which of the following statements is true ?
(a) Doubling the concentration of the solution doubles the
observed and specific rotation (b) CH 3  CH  CH  CH 2  NO 2
(b) Doubling the concentration of the solution halves the
observed and specific rotation (c)  C2 H5 2 C  N  OH

(c) Doubling the concentration of the solution doubles the (d) Ph  N  N  OH

observed rotation without affecting the specific rotation
(d) Doubling the concentration of the solution and doubling
the length of the tube increases the observed rotation
by four times.
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 162
55. Which of the following will show optical isomerism as well 59. Which out the following are non-resolvable?
as geometrical isomerism?

(a) (b)
(a)

(b)

(c) (d)

(c)

60. Select correct statements :

(d)
(a) both give colour

56. Identify the compound, which has a stereocenter here. with netural FeCl3 solution.

(b) 2–pentanone and 3–pentanone are position as well as

metamers
(c) Product formed when benzaldehyde reacts with
(a) (b) hydroxylamine shows geometrical isomerism
(d) 1, 2–dibromocyclohexane shows geometrical and optical
isomerism

Numeric Value Type Questions

(c) (d) 61. Find out the total number of stereocentre in the given com-
pound.

57. Which of the following cyclopentane derivative is/are

optically active ?
62. How many chirality centers are present in the following molecule

(a) (b)

63. Calculate the total number of dichloro derivatives of

(c) (d) cyclobutane. Fill the answer in the box.

X = Total number of dichloro derivatives.

58. Which dimethylcyclobutane is/are optically inactive ?
Y = Total number of optically active products.
(a) trans–1, 2 (b) trans–1, 3
(c) cis–1, 2 (d) cis–1, 3
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 163
Z = Total number of meso forms.
64. How many different isomers (including stereo isomers) of (4)
a monocarboxylic acid with molecular formula C6H12O2, on
decarboxylation with soda lime will produce the same n-
Assertion Reason
pentane?
(A) If both Assertion and Reason are correct and
65. Total number of isomers for C 4 H 6 Br 2 containing
cyclobutane ring are (including stereoisomer) ? Reason is the correct explanation of Asser-
tion.
(B) If both Assertion and Reason are true but
Reason is not the correct explanation of
66. (a) (x) (Number of plane of symmetry) Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
69. Assertion (A) : 1,2-dichloro cyclopropane show
geometrical isomerism
(b) (y) (Number of mesoisomer)
Reason (R) : It has restricted rotation of atoms about a
covalent bond
Sum of (x + y = ?) (a) A (b) B
(c) C (d) D
70. Assertion (A) : Compound possessing same molecular
67. formula but differing in their physical and chemical
properties are called isomers.
Reason (R) : Rearrangement reactions produce isomers.
Number of stereoisomer are
(a) A (b) B
68. Arrange in decreasing order of enolization of the following
compounds (c) C (d) D
71. Assertion (A) : Structural isomers have different physical
and chemical properties.
(1)
Reason (R) : Structural isomers have different bonding
pattern.
(a) A (b) B
(2)
(c) C (d) D
72. Assertion (A) : Alkenes containing more than three carbons
(3) exhibit chain isomerism.
3
Reason (R) : All the carbon atoms in alkenes are sp –
hybridized.
(a) A (b) B
(c) C (d) D
73. Assertion (A) : Meso–tartaric acid is optically active.
Reason (R) : Optically active molecule is a molecule that
cannot be superimposed on its mirror image
(a) A (b) B
(c) C (d) D
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 164
74. Assertion (A) : Both cis-1,3-Dimethyl cyclobutane and
trans-1,3-dimethyl cyclobutane are optically inactive.
Reason (R) : cis-1,3-dimethyl cyclobutane has the plane of (C) (r) E
symmetry, whereas trans form has the centre of symmetry.
(a) A (b) B
(c) C (d) D (D) (s) R
75. Assertion (A) : Cyclobutane is less stable than cyclopentane.
Reason (R) : Presence of ‘bent bond’ causes loss of orbital 79. Match the terms in column I with properties in column II.
overlap.
Column – II Column – II
(a) A (b) B
(A) Enantiomers (p)Can be separated into
(c) C (d) D enantiomers
76. Assertion (A) : Enantiomers differ in their chemical action (B) Diastereomers (q) Have different actions on
with other enantiomer.
enantiomer
Reason (R) : A pair of enantiomers have different orienta-
(C) Racemic mixture (r) Have different action on
tion of collision with another enantiomer forming different
transition state. achiral compounds
(a) A (b) B (D) Meso form (s) Have permanent optical
(c) C (d) D inactivity
77. Assertion (A) : 1,3-dichloro propadiene rotate plane polar- 80. Match the structures in column I with the properties in
ized light. column II.
Reason (R) : The molecules of 1,3-dichloro propadiene are Column – I Column – II
dissymmetric
(a) A (b) B
(c) C (d) D (A) (p) Has plane of symmetry
Match the Following
Each question has two columns. Four options are
given representing matching of elements from Col-
umn-I and Column II. Only one of these four op- (B) (q) Has axis of symmetry
tions corresponds to a correct matching.For each
question, choose the option corresponding to the
correct matching.
78. Column – I Column – II (C) (r) Has centre of symmetry
Compounds Characteristics

(A) (p) S (D) (s) Rotate plane polarized light

(B) (q) Z
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 165
81. Match the molecule in column I with type of stereoisomer- 83. Which of the following amines can be used for the separa-
ism shown by them in column II. tion of the above-mentioned racemic mixture?
Column – I Column – II NH2 NH2
(A) 2,3-dichlorobutane (p) Enantiomerism
(a) H3C H (b) H CH3
(B) 2-methyl-3-pentenoic acid (q) Diastereomerism
C2H5 CH3
(C) 2-butanol (r) Meso form
(D) 1,3-dichloro propadiene (s) Conformational NH2
N
82. Consider the following Fischer projections and match the (c) (d) H CH3
pair in column I with the relation in column II.
NH2
84. What would be the stereometric relations between the
products formed when the above-mentioned racemic
mixture is allowed to react with desired amine of the previous
question in order for separation of racemic mixture?
(a) The products would be identical
(b) The products would be a pair of enantiomer
(c) The products would be a pair of diastereomers
(d) The products would not be stereoisomers

Use the following passage, to anwers Q.85 to Q.87

Passage.
An organic compound having only C, H atoms has a
Column – I Column – II molecular wt. 86. By nature it is a liquid compound and it is
capable of showing chain, position isomerism. It can also
(A) I + II (p) Enantiomers show free radical halogenation reaction also.
(B) I + III (q) Diastereomers 85. How many structural isomers of C6H14 are possible ?
(C) II + IV (r) Identical (a) 3 (b) 4
(D) I + IV (c) 5 (d) 6
Paragraph Type Questions 86. How many of it’s structural isomers is/are optically active ?
Use the following passage, to anwers Q.83 to Q.84 (a) Zero (b) 1
Passage.
(c) 2 (d) 3
A racemic mixture containing following enantiomers are to
be separated into pure enantiomers by reacting with a pure 87. Which of the following alkane on single mono chlorination
enantiomer. can give 3–mono substituted products ?

COOH COOH (a) 2–Methylpentane (b) n–Hexane

H3C H H CH3

C2H5 C2H5

I II
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 166
(c) 2, 2–Dimethylbutane (d) both (b) & (c)

Use the following passage, to anwers Q.88 to Q.90

(b)
Passage.
A solution contain three stereoisomers of 2,3-dihydroxy
butanedioic acid. On fractional crystallization of this
solution, two fractions. Fraction–I and Fraction–II are (c)
separated. Fraction-I on reaction with (+)-2-butanamine
gives a single salt while Fraction-II on reaction with the
same (+)-2-butanamine gives a mixture of two salts.
Answer the following three questions based on the (d)
above information.
88. What can be accurately predicted about the molecules of 92. The total number of stereoisomers possible for (A) is:
fraction-I?
(a) 8 (b) 7
(a) Molecules of fraction-I are enantiomers
(c) 6 (d) 4
(b) Molecules of fraction-I are meso compound
93. If the stereochemistry about the double bond in (A) is cis,
(c) Molecules of fraction-I are in racemic form the total number of stereoisomers for (A) is:
(d) Molecules of fraction-I has no chiral centre (a) 2 (b) 3
89. What is the relationship between the molecules of frac- (c) 4 (d) 5
tion-I with the molecules of fraction-II
94. If the stereochemistry about the double bond in (A) is cis,
(a) They are enantiomers the total number of enantiomers for (A) is
(b) They are identical (a) None (b) 2
(c) They are diastereomers (c) 4 (d) 6
(d) They are diastereomers as well as optically active
Subjective Type Questions
90. What is the relationship between the two different salts
obtained from fraction-II? 95. Write tautomeric forms of phenol.

(a) They are structural isomers 96. Write the structure of all the possible isomers of
dichloroethene. Which of them will have zero dipole
(b) They are enantiomers moment?
(c) They are diastereomers 97. Write structural formulae for the isomeric alcohols having
the molecular formula C4H10O.
(d) They are conformers
Fill in the Blanks
Use the following passage, to anwers Q.91 to Q.94
Passage. 98. Isomers which are .............. mirror images are known as
.............. (superimposable, non-superimposable,
An organic compound (A) (C10H20) on reductive ozonoly- enantiomers, diastereomers, epimers)
sis gives 2-methyl butanal. Based on this information, an-
swer the following questions. 99. .............. ring is most strained. (Cyclopropane, Cyclobutane,
Cyclopentane).
91. Compound (A) is
100. The IUPAC name of succinic acid is .................

(a)
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 167

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS

Objective Questions I [Only one correct option] 6. The number of isomers of C6H14 is (2007)
1. The number of isomers for the compound with molecular (a) 4 (b) 5
formula C2BrCFI is (2001)
(c) 6 (d) 7
(a) 3 (b) 4
7. The correct order of acidity for the following compounds
(c) 5 (d) 6 is (2013)
2. Which of the following compounds exhibits, stereoisomerism ?
(2002)
(a) 2–Methyl But–1–ene
(b) 3–Methyl But–1–yne
(c) 3–Methyl Butanoic Acid
(d) 2–Methyl Butanoic Acid (a) I > II > III > IV (b) III > I > II > IV

3. (c) III > IV > II > I (d) I > III > IV > II
8. Newman projections P, Q, R and S are shown below :

C2 is rotated anti-clockwise 120° about C2––C3 bond. The

resulting conformer is (2004)
(a) partially eclipsed (b) eclipsed
(c) gauche (d) staggered
4. The number of stereoisomers obtained by bromination of
trans-2-butene is (2007)
(a) 1 (b) 2
(c) 3 (d) 4 Which one of the following options represents
identical molecules? (2020/Shift-1)
5. Statement – 1 : Molecules that are non-superimposable on (a) P and Q (b) Q and S
their mirror images are chiral.
(c) Q and R (d) R and S
Statement – 2 : All chiral molecules have chiral centres.
(2007)
(a) Statement – 1 is True, Statement – 2 is True; Statement
– 2 is a correct explanation for Statement – 1.
(b) Statement – 1 is True, Statement – 2 is True; Statement – 2
is not a correct explanation for Statement – 1.
(c) Statement – 1 is True, Statement – 2 is False.
(d) Statement – 1 is False, Statement – 2 is True.
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 168
9. The Fischer projection of D-erythrose is shown below.

(c) (d)

Objection Question II
[One or more than one correct option]
D-Erythrose and its isomers are listed and P, Q, R, and 11. The correct statement(s) about the compound given below
S in Column-I. Choose the correct relationship of P, Q, is (are) (2008)
R and S with D-erythrose from Column-II.

(a) the compound is optically active

(b) the compound possesses centre of symmetry
(c) the compound possesses plane of symmetry
(d) the compound possesses axis of symmetry
12. The correct statement(s) concerning the structures E, F
and G is (are) (2009)

(2020/Shift-1)
(a) E, F and G are resonance structures
(a) P  2, Q  3, R  2, S  2
(b) E, F and E, G are tautomers
(b) P  3, Q  1, R  1, S  2
(c) F and G are geometrical isomers
(c) P  2, Q  1, R  1, S  3 (d) F and G are diastereomers
(d) P  2, Q  3, R  3, S  1 13. The correct statement (s) about the compound
H3C(HO) HC–CH=CH–CH(OH)CH3 (X) is (are) (2009)
10. Among the following, the conformation that
corresponds to the most stable conformation of (a) The total number of stereoisomers possible for X is 6.
meso-butane-2,3-diol is (2021) (b) The total number of diastereomers possible for X is 3.
(c) If the stereochemistry about the double bond in X is
trans, the number of enantiomers possible for X is 4.
(d) If the stereochemistry about the double bond in X is
(a) (b)
cis, the number of enantiomers possible for X is 2.
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 169

14. The IUPAC name(s) of the following compound is (are) Choose the correct statement(s). (2020/Shift-2)
(2017) (a) The order of basicity is II > I > III > IV.
(b) The magnitude of pK b difference between I and II
is more than that between III and IV.
(c) Resonance effect is more in III than in IV.
(a) 4-chlorotoluene (d) Steric effect makes compound IV more basic than
(b) 4-methylchlorobenzene III.
(c) 1-chloro-4-methylbenzene
Numeric Value Type Questions
(d) 1-methyl-4-chlorobenzene
17. Give the total number of cyclic structural as well as stereo
15. With respect to the compounds I-V, choose the isomers possible for a compound with the molecular
correct statement(s). (2020/Shift-1) formula C5H10. (2009)
18. Total number of isomers considering both structural
and stereoisomers, of cyclic ethers with the molecular
formula C4H8O is__________ (2019/Shift-2)
Subjective Type Questions
19. (a) Draw Newman’s projection for the less stable staggered
form of butane.
(b) Relatively less stability of the staggered form is due to
(i) Torsional strain
(ii) van der Waals’ strain
(iii) Combination of the above two (2004)
20. obs   i x i

where i is the dipole moment of stable conformer and xi is

(a) The acidity of compound I is due to delocalization the mole fraction of that conformer. (2005)
in the conjugate base.
(a) Write stable conformer for Z – CH2 – CH2 – Z in
(b) The conjugate base of compound IV is aromatic. Newman’s projection.
(c) Compound II becomes more acidic, when it has a –
If solution = 1.0D and mole fraction of anti form = 0.82, find
NO2 substituent.
gauche
(d) The acidity of compounds follows the order
(b) Write most stable meso conformer of (CHDY)2
I > IV > V > II > III.
16. Consider the following four compounds I, II, III, and IV. If (i) Y = CH3 about C2–C3 rotation and
(ii) Y = OH about Cl-C2 rotation.
GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM 170

Note:

Find Answer Key and Detailed Solutions at the end of this book

GENERAL ORGANIC CHEMISTRY

(Revision) & ISOMERISM
Please share your valuable feedback by
scanning the QR code.
ALKYL AND ARYL HALIDES
 Chapter 04 172

ALKYL AND ARYL HALIDES

1. INTRODUCTION

The replacement of hydrogen atom(s) in an aliphatic or aromatic Classification of alkyl halides based on type of carbon atom to
hydrocarbon by halogen atom(s) results in the formation of alkyl
which the halogen atom is attached :
halide (haloalkane) and aryl halide (haloarene), respectively. Many
halogen containing organic compounds occur in nature and some
of these are clinically useful. These classes of compounds find
wide applications in industry as well as in day to-day life.

1.1 Classification of Organic Halogen Compounds

Organic halogen compounds can be classified as follows :
1. Based on degree of carbon atom containing halogen atom
2. Based on number of Halogens
3. Based on the hybridisation of carbon attached with halogen

X may be F, Cl, Br or I.

Classification of organic halogen compounds

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
173

1.2 Nomenclature of Alkyl Halides

After getting idea about classification of halogenated organic compounds, now we shall learn how these compounds are named.

Nomenclature of alkyl halides

1.3 Nomenclature of Aryl Halides

Haloarenes are the common as well as IUPAC names of aryl halides. For dihalogen derivatives, the prefixes o-, m-, p- are used in
common system but in IUPAC system, the numerals 1,2; 1,3 and 1,4 are used.

Nomenclature of aryl halides

Common and IUPAC Names of some Halides

Structure Common name IUPAC name

CH3CH 2 CH  Cl  CH3 sec-Butyl chloride 2-Chlorobutane

 CH3 3 CCH2 Br neo-Pentyl bromide 1-Bromo-2,2-dimethylpropane
 CH3 3 CBr tert-Butyl bromide 2-Bromo-2-methylpropane
CH 2  CHCl Vinyl chloride Chloroethene
CH 2  CHCH 2 Br Allyl bromide 3-Bromopropene

o-chlorotoluene 1-Chloro-2-methylbenzene
or
2-Chlorotoluene

Benzyl chloride Chlorophenylmethane

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
174

1.4 Nature of C-X Bond

Halogen atoms are more electronegative than carbon, therefore, carbon-halogen bond of alkyl halide is polarised; the carbon atom
bears a partial positive charge whereas the halogen atom bears a partial negative charge.

As we go down the group in the periodic table, the size of halogen atom increases. Fluorine atom is the smallest and iodine atom is the
largest. Consequently, the carbon-halogen bond length also increases from C—F to C—I.
Carbon-Halogen (C-X) Bond Length, Bond Enthalpies and Dipole Moments

Bond Bond length/pm C-X bond enthalpies/ kJ mol-1 Dipole moment/Debye

CH 3  F 139 452 1.847
CH3  Cl 178 351 1.860
CH 3  Br 193 293 1.830
CH 3  I 214 234 1.636

Now, lets discuss few terms related to this chapter

2. REAGENTS : ELECTROPHILES AND

NUCELOPHILES

In general, reaction is conversion of reactants into products and

reagent is electron rich or deficient species which attacks on
substrate.

Types of Electrophiles
2.2 Nucleophiles
Features related to nucleophile :
 Positive charge loving species
 Electron rich
 Attacks electron deficient centres
 Electron pair donors
 Lewis Bases
Types of Reagents

2.1 Electrophiles

Features related to electrophile :

 Electron loving species
 Electron deficient
 Attacks electron rich centres
 Electron acceptors
 Lewis acids
Types of Nucleophiles

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
175

3. SOLVENTS Examples
Acidic Strength :
Solvents are liquids that are used to dissolve other
CH4 < NH3 < H2O < HF
substances.Solvents work on the principle of “like dissolves like”
For example, water is a polar solvent and it will dissolve salts and Basic Strength and Nucleophilicity :
other polar molecules, but not non-polar molecules like oil. 
CH 3  
NH 2   OH  F 
Polar solvents have large dipole moments, they contain bonds (d) If the attacking atoms are different in size, the nucleophi-
between atoms with very different electronegativities, such as licity depends on the solvents. However, in gaseous phase
oxygen and hydrogen. Non polar solvents contain bonds between nucleophilicity parallels basicity.
atoms with similar electronegativities, such as carbon and (e) Nucleophilicity is inversly proportional to stability of an-
hydrogen. O
Solvents can be classified as follows : ||
ion. R  C  O  is a weaker nucleophile as it is resonance
1. Non-polar solvents stabilized.
2. Polar solvents (f) Steric factor limits nucleophilicity

(g) A strong base can be made a good leaving agent e.g.

Oxygen containing group like OH can be made a weak
base in acidic medium by protonation & become a better

leaving agent  OH 2 .
Types of solvents
(h) Protic solvent : These solvents have a hydrogen atom
attached to an atom of a strongly electronegative element
4. NUCLEOPHILICITY VS BASICITY (e.g. oxygen). Molecules of protic solvent can, therefore
(a) Nucleophilicity & basicity will be parallel if the comparing form hydrogen bonds to nucleophiles as :
nucleophile have same attacking atom e.g.

O
||
CH 3 O  OH   CH 3  C  O
(b) Negatively charged nucleophiles are stronger than neu-
tral nucleophiles. e.g.
OH   H 2 O or NH 2  NH 3
(c) Electrons on larger atoms are less tightly bound by the Nucleophile forming hydrogen bonds with
nucleus and are more polarisable and more readily avail- molecules of protic solvent
able to carbon & will be better nucleophile. But they will be A small nucleophile which is having high charge density than the
weaker base as their bond with smaller H-atoms will be large nucleophile is strongly solvated and this solvation hinders
weaker & their conjugate acids will be more reactive. If the the direct approach to the nucleophilic centre. Hence the smaller
attacking atoms are of same size, the stronger bases are nucleophile doesn’t act as a good nucleophile as the larger one.
better nucleophile. (In a period basicity of anions decreases) Hence in protic solvent nucleophilicity is reverse of basicity.

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
176

reagent. Reactions in organic chemistry are classified into three

categories :
1. Addition reactions
2. Substitution reactions
(i) Aprotic solvents : These are the polar solvents that don’t
have H atom, capable of forming H-bonds e.g. 3. Elimination reactions
5.1 Addition Reaction
This reaction involves addition of groups to a  bond.

Dimethyl sulphoxide N,N-Dimethyl formamide

(DMSO) (DMF) 5.2 Substitution Reaction
This reaction involves the replacement of an atom or a group of
atoms by another atom or group of atoms.

N,N-Dimethyl acetamide `

(DMA) 5.3 Elimination Reaction

These solvents dissolve ionic compounds and solvate the This reaction involves the loss of atoms or groups of atoms to
cations. form an unsaturated compound.

6. REACTIONS OF ALKYL HALIDES

As C  X bond is polar and X being good leaving group, in

presence of electron rich reagent (Nucleophile or Base) it show
two characteristic reactions viz. Nucleophilic substitution (SN)
and elimination reaction (E).

Solvated sodium cation in DMSO solvent

Now the naked anions are highly reactive as a nucleophile and
now nucleophilicity follows the basicity e.g.
However these substitution and elimination reactions takes place
via various mechanism: hence to know them in details, we need to
study ‘Reaction Mechanism’.

5. REACTIONS IN ORGANIC CHEMISTRY

There are various types of reactions possible in organic

compounds depending on reaction conditions and attacking

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
177

Stereochemistry of SN2 reaction :

7. NUCLEOPHILIC SUBSTITUTION REACTIONS
In SN2 the nucleophile hits the carbon on the side, opposite to the
Nucleophile is a reacting species which attacks at positively side bonded to the leaving group, the carbon is said to undergo
charged carbon backside attack.
The best way to visualize the movement of the groups bonded to
the carbon at which substitution occurs is to picture an umbrella
that turns inside out. This is called inversion of configuration or
we can say that SN2 mechanism occurs with the inversion of
configuration.
The replacement of halogen atom (leaving group) by the attack-
ing nucleophile is called nucleophilic substitution reaction at sp3
carbon. This reaction was studied in great detail and two extreme
mechanisms have been outlined to explain the course of the reac-
tion. Stereochemistry of SN2 reaction

1. Bimolecular nucleophilic substitution reaction (SN2) 7.2 Substitution Nucleophilic Unimolecular - SN1
2. Unimolecular nucleophilic substitution reaction (SN1) Mechanism :
7.1 Substitution Nucleophilic Bimolecular - SN2 Step 1 :

Mechanism :

Step 2 :

Key Features of SN2 Mechanism :

1. Single step reaction.
2. Rate = k [RX] [Nu]
3. No intermediate is formed. Reaction goes through a
transition state.
Key Features of SN1 Mechanism :
4. Rearrangement is not observed.
1. Two step reaction. First step is the formation (and
5. Inversion of configuration is observed (WALDEN inversion). rearrangement) of carbocation while second step is the
6. Order of reactivity of alkyl halides : attack of nucleophile on the carbocation.
CH3X > 1° > 2° > 3° 2. Rate = k [RX]
This can be attributed to the steric hinderance to back side 3. Carbocation is formed.
attack of nucleophile. 4. Rearrangement is commonly observed.
7. Favoured by polar aprotic solvents. 5. Racemic mixture is observed.
6. Order of reactivity of alkyl halides :
3° > 2° > 1° CH3X
This can be attributed to the stability of the carbocation
that is formed.
7. Favoured by polar protic solvents.

Energy profile diagram of SN2 mechanism

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
178

nucleophile is possible from both sides. It means we will be getting

both the products with the same and the opposite configurations
and hence racemisation will occur but we can’t say that 100%
racemisation will occur because there is no surety that we will be
getting both the products in equal amount. Still we can say that
racemisation will take place.

Energy profile diagram of SN1 mechanism

Stereochemistry of SN1 reaction :
SN1 reaction takes place in two steps. In first step formation of
carbocation takes place and in second step attack of nucleophile Stereochemistry of SN1 reaction
takes place. The carbocation has planar shape so attack of

7.3 Comparison between SN1 & SN2 reactions

SN1 vs SN2 reactions

S N1 S N2

SN1 is a unimolecular reaction. SN2 is a bimolecular reaction.

It follows a 1st order kinetic mechanism. It follows the 2nd order kinetic mechanism.

SN1 involves two steps. SN2 is a single-step process.

In SN1, the rate of reaction depends on the In SN2, the rate of reaction depends on the
concentration of the substrate. concentration of both the substrate and the
nucleophile.

In SN1 as the leaving group leaves, the substrate In SN2, the reaction happens in a single transition
forms a carbocation intermediate. state.

Optically active substrate becomes optically inactive SN2 involves inversion reaction.
and half of the optically active substrate becomes
similar.

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
179

Step 2 :
8. ELIMINATION REACTIONS

The removal of halogen from the carbon to which it is attached

along with the removal of hydrogen from adjacent carbon is called
, -elimination or simply elimination. We will discuss following
two mechanisms in detail in this part:
1. Bimolecular Elimination (E2)
2. Unimolecular Elimination (E1)
8.1 Elimination Bimolecular - E2 Key Features of E1 Mechanism :
Mechanism : 1. Two step reaction. First step is the formation of carbocation
while second step is the loss of proton by a base.
2. Rate = k [RX]
3. Carbocation is formed.
4. Rearrangement is commonly observed.
Key Features of E2 Mechanism :
5. Observed in presence of weak bases.
1. Single step reaction.
6. Order of reactivity of alkyl halides :
2. Rate = k [RX] [Base]
3° > 2° > 1°
3. No intermediate is formed. Reaction goes through a transition
This can be attributed to the stability of carbocation as well
state.
as the stability of alkene formed.
4. Rearrangement is not observed. 7. Favoured by protic solvents.
5. Observed in presence of strong bases. 8.3 Saytzeff vs. Hofmann Rule
6. Order of reactivity of alkyl halides : 3° > 2° > 1° When alkene is formed by elimination of alkyl halides, the orien-
This can be attributed to the stability of alkene formed. tation of the double bond formed is governed by two rules.
7. Favoured by aprotic solvents. 8.3.1 Saytzeff’s Rule/Zaitsev Rule

8.2 Elimination Unimolecular - E1 This rule suggests the formation of more stable alkene as the
major product and therefore more substituted double bond.
Mechanism :
Reactions following this rule are said to be thermodynamically
Step 1 : controlled.
Example

8.3.2 Hofmann Rule

This rule suggests the formation of less stable alkene as the major
product and therefore less substituted double bond. In such cases,
the more acidic  -hydrogen is abstracted to produce alkene. Such
reactions are said to be kinetically controlled. Hoffmann product
is formed when the Base is Bulky.

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
180
Example 8.4 Effect of Temperature
High temperature favours elimination while low temperature
favours substitution reaction.

8.5 Comparison between E1 & E2 reactions

E1 vs E2 reactions

Supporting factors E1 E2

Base Weak base Strong base required

Solvent Good ionizing solvent Wide variety of solvent

Substrate 3 o > 2o > 1 o 3 o > 2o > 1 o

Leaving group Better one required Better one required

Kinetics K[R - X], 1st order K[R - X] [Base], 2nd order

Orientation Saytzeff alkene Saytzeff alkene

Stereochemistry No special geometry is Transition state must be anti coplanar

required

9. NUCLEOPHILIC SUBSTITUTION VS
ELIMINATION REACTIONS

Any species that acts as a base can also act as a nucleophile. To

understand how elimination and substitution compete with each
other, we compare the nucleophilic behaviour with the basic
behaviour.
Elimination vs substitution reactions

Alkyl halide SN2 vs E2 SN1 vs E1

1o Alkyl halide Primarily substitution unless there Usually does not undergo E reaction
is steric hindrance in the alkyl
halide or nucleophhile in which case
elimination in fovaoured.

2o alkyl halide Both substitution and eimination, Both substitution and elimination,
the stronger and bulkier the base the higher the temperature the greater the
and higher the temperature greater the percentage of elimination.
greater the % of elimination

3o alkyl halide Only elimination Both substitution and elimination

high temperature favours
elimination.

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
181

5. Alcohol
10. ALKYL HALIDES

10.1 Preparation of Alkyl Halides

1. Alkanes

RH 
Cl2
h
RCl  HCl

This method gives a mixture of mono, di & trihalides.

2. Alkenes
(i) R  CH  CH 2  X 2 
CCl4
 R  CH  CH 2 Lucas test
| |
X X
X2  Br2 ,Cl2 ,I2
(ii) R  CH  CH 2  H  X 
 R  CH  CH 3 Order of reactivity of alcohol: 3o > > 2o > 1o
| 6. Carbonyl Compound
X
Markovnikov
addition
X
|
(iii) (a) R  CH 2  CH  CH 2  X2
 R  CH  CH  CH 2
400o  500o C
Allylic substituion 7. Carboxylic Acids
(b) R  CH 2  CH  CH 2 
 R  CH  CH  CH 2
NBS

|
Br

(iv)

3. Alkynes

4. Alkyl Halides (Halogen Exchange reaction)

(i) Finkelstein Reaction
R  Br  NaI 
acetone
 R  I  NaBr Methods of preparation of Alkyl halides
R  Cl  NaI 
acetone
 R  I  NaCl 10.2 Physical Properties
(ii) Swartz Reaction Alkyl halides are colorless when pure. However, bromides and
iodides develop color when exposed to light. Many volatile
R  Br  AgF 
DMSO
 R  F  AgBr
Polar
aprotic
halogen compounds have a sweet smell. The boiling points of
organohalogen compounds are comparatively higher than the
corresponding hydrocarbons because of strong dipole-dipole and
van der Waals forces of attraction. These are slightly soluble in
water but completely soluble in organic solvents.

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
182
aq.KOH
10.3 Reactions of Alkyl Halide R  X  R  OH
alc KOH
1. Coupling Reaction R  X 
 Alkene
(a) Wurtz Reaction
Et O
2RX  2Na 
2 R  R  2NaX
(b) Grignard Reagent

R  X  R  MgX 
 R  R  MgX 2
(c) Corey-House Synthesis

R  X  2Li 
 R  Li  LiX

2R  Li  CuI 
 R 2 CuLi  LiI

R 2 CuLi  R   X 
 R  R   Cu  LiX
2. Reaction with Ammonia Reactions of Alkyl Halide
C2 H5OH
R X NH3   R  NH 2 11. ARYLHALIDES/HALOARENES
1 Amine

NOTE 11.1 Preparation of Aryl Halide/Haloarenes

If alkyl halide is in excess, then 1° amines and even (a) Halogenation of Arenes
quaternary salts are also formed.

This reaction is called Hofmann ammonolysis of alkyl

halides. (b) Sandmeyer Reaction
3. Reaction with KCN
R  X  KCN 
 R  CN KX
Alkyl nitrile

4. Reaction with AgCN

  (c) Diazotization
R  X  AgCN 
 R  N  C
Alkyl isonitrile

5. Reaction with NaNO2

R  X  NaNO 2 
 R  O  N  O  NaX
6. Reaction with AgNO 2

RX  AgNO 2 
 R  NO 2  AgX
7. Reaction with LiAlH 4

R  X  LiAlH 4 
 R  H (Reduction)
(d) Schiemann Reaction
8. Williamson’s Synthesis
S 2
R  X  R  O  Na 
N R  O  R  NaX
9. Aq. KOH & Alc. KOH

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
183

12. POLYHALOGEN COMPOUNDS

12.1 Di-Halides

Methods of preparation of Aryl Halide/Haloarenes 12.1.1 Preparation

(a) Halogenation of Alkenes & Alkynes
11.2 Reactions of Aryl Halide/Haloarenes CH 2  CH 2  X 2  CH 2 X  CH 2 X Vicinal Dihalide
(a) Electrophilic Aromatic Substitution Reaction : Halogens
are weakly deactivating and ortho/para directing. CH  CH  2HX  CH 3 CHX 2 Geminal Dihalide
(b) Formation of Aryl Grignard Reagent : (b) PCl5 with Diols & Carbonyl Compounds

Reactivity order : Ar  I > Ar  Br > Ar  Cl > Ar  F

12.1.2 Properties
(c) SNAr  Aromatic Nucleophilic Substitution Reaction
(a) Alcoholic KOH : (Dehydrohalogenation)

XCH 2 CH 2 X 
Alcoholic
KOH
 CH  CH

CH3CHX 2 
Alcoholic
KOH
 CH  CH

(b) Zinc Dust : (Dehalogenation)

(d) Benzyne Mechanism (Elimination Addition
Mechanism)-Strong bases such as Na, K and amide react XCH 2 CH 2 X Zn
Alcohol
 CH 2 == CH 2  ZnX 2

readily with aryl halides.

CH3CHX 2 Zn
Alcohol
 CH3  CH == CH  CH3

(c) Action of aq. KOH : (Alkaline Hydrolysis)

(i) Vicinal Dihalides

Reactions of Aryl Halides/Haloarenes

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
184

(ii) Gem Dihalides (iii) Carbon Tetrachloride

Fe  H 2 O
CCl 4  2[H] 
HCl
 CHCl3  HCl

(iv) Chlorination of Methane at 370C

370 C
CH 4  3Cl2  
Diffused Sunlight
 CHCl3  3HCl

(B) Reactions
(i) Oxidation
Chloroform in presence of light and air (O2) forms a highly
poisonous gas, Phosgene.
NOTE 2CHCl3  O2 
light
 2COCl2  2HCl
The above reaction is used to distinguish between Phosgene

gem and vicinal dihalides.

12.2 Tri-Halides & Tetra-Halides

NOTE
1% Ethanal is added and then chloroform is stored in
CHCl3 CHBr3
brown bottles, filled upto brim to stop the above
Chloroform Bromoform decomposition.
(liquid) (liquid)
CHI3 CHCl3 (ii) Carbylamine Reaction
Iodoform Carbon Tetrachloride RNH2 + CHCl3 + 3KOH  RNC + 3H2O + 3KCl
(yellow solid) (liquid)
C6 H 5 NH 2  CHCl3  3KOH  C 6 H 5 NC  3H 2 O  3KCl
12.2.1 Chloroform : CHCl3
Isocyanides (carbylamines) have a very disagreable smell, so the
(A) Preparation
above reaction is used as a test of chlororom and test of 1° (ali-
(i) Ethyl Alcohol : (using NaOH/Cl2 or CaOCl2) phatic and aromatic) amines.
(iii) Hydrolysis
CH 3 CH 2 OH 
Cl2
2HCl
 CH 3 CHO 
3Cl2
3HCl
 Cl3CCHO
Ethanol Ethanal Trichloroethanal
(Chloral)

Ca  OH 2  2Cl3 C  CHO   HCOO  2 Ca  2 CHCl3

Calcium Chloroform
formate

NOTE
Pure form of chloroform is prepared from chloral by (iv) Formation of Acetylene
treating it with NaOH.
2CHCl3  6Ag 
 CH  CH  6AgCl
Acetylene

(ii) Methyl Ketones (v) Formation of Chloropicrin

CHCl3  HNO3 
 CCl3 NO 2
Chloropicrin
(an insecticide)

(vi) Formation of Chloretone

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
185

12.2.2 Iodoform: CHI3 (ii) Reduction

(A) Preparation : CCl4  2[H] 
Fe/ H 2 O
CHCl3  HCl
C 2 H 5 OH  3I2  3Na 2 CO3 (iii) Hydrolysis

CHI 3   3HCOONa  3NaI  2CO 2
Yellow solid

CH 3 COCH 3  3I 2  2Na 2 CO3

 (iv) Action of HF
CHI3   2NaI  CH 3 COONa  H 2 O  2CO 2 
CCl 4  4HF 
SbF6
 CCl2 F2  2HCl
Freon

NOTE 12.2.4 Vinyl Chloride : CH2 = CHCl

This reaction is known as Iodoform reaction or Iodo Vinyl group CH2 = CH
form test. Since the iodoform is a yellow colored solid,
(A) Preparation :
so the iodoform reaction is used to test ethyl alcohol,
acetaldehyde, sec. alcohols of R(CH3)CHOH (methyl (i) CH  CH  HCl 
 CH 2  CHCl
alkyl carbinol) and methyl ketones (RCOCH3), because
all these form iodoform. The side product of the
2 ClCH 2 Cl   CH 2  CHCl  KCl  H 2 O
KOH(alc.)
(ii) CH
iodoform reaction, sodium carboxylate is acidified to Vicinal Dihalide

produce carboxylic acid (RCOOH). 600  C

(iii) CH 2  CH 2  Cl 2   CH 2  CHCl  HCl

12.2.3 Carbon Tetrachloride : CCl4 (B) Reaction :

(A) Preparation : (i) CH 2  CHCl 2  alc.KOH 

 CH  CH  HCl
Acetylene

(i) CH 4  4Cl 2  CCl 4  4HCl

hv

excess
diffused Halogen atom in vinyl chloride is quite stable and does not re-
spond to nucleophilic substitution reactions easily. It is due to
(ii) CS2  3Cl 2 
AlCl
Fe/I 2
 CCl 4  S2 Cl 2 resonance stabilisation of vinyl chloride.

S2Cl2 is separated by fractional distillation. It is then treated with

more CS2 to given CCl4 washed with NaOH and distilled to obtain
pure CCl4. 12.2.5 Allyl Chloride : H2C = CHCH2Cl
2S2 Cl 2  CS2 
 CCl 4  6S (A) Preparation :
o
(i) H 2 C=CHCH 3 +Cl2   CH 2 =CHCH 2 Cl
400 C 500-600 C
(iii) CH 3 CH 2 CH 3  Cl2 
70-100 atm
 CCl4  HCl  C2 Cl6
Propene

(ii) H 2 C  CHCH 2 OH  PCl3  H 2 C  CHCH 2 Cl 

NOTE Allyl alcohol

CCl4 is a colourless and poisonuous liquid which is POCl3  HCl

insoluble in H2O. It is a good solvent for grease and
(B) Reactions :
oils. CCl4 is used in fire extingusher for electric fires as
Pyrene. It is also used as an insecticide for bookworms. (i) Addition Reactions

(B) Reactions : CH 2  CH  CH 2 Cl  Cl2 

CCl4
 CH 2 ClCHClCH 2 Cl
(i) Oxidation
CH 2  CH  CH 2 Br  HBr 
 CH3CHBrCH 2 Br
500 C
CCl4  H 2 O   COCl2  2HCl 1, 2-Dibromopropane
Steam
The addition follows Markonikov’s Rule. However in presence of
peroxides antimarkovnikov reaction is followed.

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
186

(i)
(ii) Nucleophilic Substitution Reactions
Since in allyl chloride, there is no resonance (unlike in vinyl chlo-
ride), nucleophilic substitution reactions take place with ease.

CH 2  CH  CH 2 Cl 
KOH(aq)
 CH 2  CHCH 2 OH  KCl (ii)

CH 2  CH  CH 2 Cl 
NH3
 CH 2  CH  CH 2 NH 2  HCl

CH 2  CHCH 2 Cl 
KCN
 CH 2  CH  CH 2 CN  KCl
(iii)
CH 2  CHCH 2 Cl  Mg 
dry
ether
 CH 2  CHCH 2 MgCl
Grignard Reagent

12.2.6 Benzyl Chloride : C6H5CH2Cl/PhCH2Cl

(A) Preparation :
(iv) Wurtz Reaction

(v) Oxidation
(B) Reactions :
The main reactions are like those of Alkyl Halides (since there is
no resonance in benzyl chloride and intermediate benzyl
carbonium ion is stable supporting S N 1 substitution).
Nucleophillic substitution reactions occur with ease unlike in case
of aryl halides (due to resonance in aryl halides).

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES
187

SUMMARY
Methods of preparation of Alkyl halides Methods of preparation of Aryl Halide/Haloarenes

Reactions of Alkyl Halide Reactions of Aryl Halides/Haloarenes

SCAN CODE
Alkyl and Aryl Halides
ALKYL AND ARYL HALIDES 188

SOLVED EXAMPLES

Example-1

For the compounds

CH3Cl, CH3Br, CH3I and CH3F, the correct order of
increasing C – halogen bond length is:
(a) CH3F < CH3Cl < CH3Br < CH3I
(b) CH3F < CH3Br < CH3Cl < CH3I
Example-4
(c) CH3F < CH3I < CH3Br < CH3Cl
(d) CH3Cl < CH3Br < CH3F < CH3I Of the four isomeric hexanes, the isomer which can give two
Ans. (a) monochlorinated compounds, is
Sol. Bond lenght  size of atom (a) 2-methylpentane
(b) 2, 2-dimethylbutane
CH 3 F  CH 3Cl  CH 3 Br  CH 3 I
(c) 2, 3-dimethylbutane
Example-2 (d) n-hexane
Ans. (c)
Write the structure of all the possible isomers of
dichloroethene. Which of them will have zero dipole Sol.
moment ?

Sol. Dichloroethene exists in 2 geometrical isomers.

Trans isomer has zero dipole

Example-3

On mixing a certain alkane with chlorine and irradiating it

with ultraviolet light, it forms only one monochloroalkane.
This alkane could be
(a) propane (b) pentane
(c) isopentane (d) neopentane
Ans. (d)

Sol. Cn H 2n+2 + Cl2 

UV
2 monochloroalkanc
ALKYL AND ARYL HALIDES 189

Example-5 Sol.

2-methyl butane on reacting with bromine in the presence of

sunlight gives mainly
(a) 1-bromo-3-methylbutane (b) 2-bromo-3-methylbutane
(c) 2-bromo-2-methylbutane (d) 1-bromo-2-methylbutane
Ans. (c)
Sol.

Example-8
Example-6
HBr reacts with under anhydrous
The reaction conditions leading to the best yield of C2H5Cl
conditions at room temperature to give
are
(a) CH3CHO and CH3Br (b) BrCH2CHO and CH3OH
UV light
(a) C2H6 (excess) + Cl2  
(c) BrCH 2  CH 2  OCH 3 (d) H 3 C  CHBr  OCH 3
Dark Ans. (d)
(b) C2H6 + Cl2 (excess) 
room temp.

UV light
(c) C2H6 + Cl2 (excess)  Sol.


UV light
(d) C2H6 + Cl2  
Example-9
Ans. (a)
Sol. During chlorination of alkane, if excess of alkane is treated Which of the following reactions will yield 2,
2-dibromopropane ?
with Cl2  g  in presence of light or heat chance of mono-
(a)
chlorination predominate.
(b)
C2 H 6  excess   Cl2 
UV light
 CH 3CH 2 Cl  HCl (c)

Example-7 (d)
Ans. (a)
Reaction of one molecule of HBr with one molecule of 1,
3-butadiene at 40°C gives predominantly Sol.

(a) 1-bromo-2-butene under kinetically controlled conditions

(b) 3-bromobutene under thermodynamically controlled
conditions
(c) 1-bromo-2-butene under thermodynamically controlled
conditions
(d) 3-bromobutene under kinetically controlled conditions
Ans. (c)
ALKYL AND ARYL HALIDES 190

Example-10 Example-14

In the presence of peroxide, HCl and HI do not give Predict the structure of the product in the following reaction
anti-Markownikoff’s addition to alkenes because:
(a) HCl is oxidizing and the HI is reducing
(b) All the steps are exothermic in HCl and HI
(c) Both HCl and HI are strong acids
(d) One of the steps is endothermic in HCl and HI
Ans. (d)
Sol.
Sol. Because one of the step is endothermic in HCl and HI ,
so furthur reaction do not occur.

Example-11

Write down the structures of the stereoisomers formed when

cis-2-butene is reacted with bromine.
Ans. (0) Example-15
Sol.

The decreasing order of the rate of the above reaction with

–
nucleophile (Nu ) A to D is
– –
[Nu = (A) PhO–, (B) AcO–, (C) HO , (D) CH3O ]
(a) D > C > A > B (b) D > C > B > A
Example-12 (c) A > B > C > D (d) B > D > C > A
Ans. (a)
The compound which reacts fastest with Lucas reagent at
Sol. More stable carbanion less will be nucleophile A and B is
room temperature is
stabilize by resonance D have highest -ve charge
(a) butan-2-ol (b) butan-1-ol concentrate on oxygen B form equivalent resonating
(c) 2-methyl propan-1-ol structure is most stable among all
(d) 2-methyl propan-2-ol Example-16
Ans. (d) The major product formed when 1,1, 1 trichloro–propane
Sol. With lucas reagent 3 alcohol react faster
0 is treated with aqueous potassium hydroxide is :
(a) 2–Propanol (b) Propyne
Example-13
(c) Propionic acid (d)1–propanol
HBr reacts fastest with Ans. (c)
(a) 2-methyl propan-2-ol (b) propan-1-ol
(c) propan-2-ol (d) 2-methyl propan-1-ol Sol.
Ans. (a)
Sol. HBr react fastest which for stable carbon
CH 3 CH 3
| |
H
H 3 C  C  CH 3  CH 3  C  CH 3
| 
OH
3 -alcohol form 3 carbocation
ALKYL AND ARYL HALIDES 191
Example-17 (c) R3C X > R2CH X > RCH2 X
(d) R2CH X > R3C X > RCH2 X
The organic chloro compound, which shows complete
stereochemical inversion during an SN2 reaction is (X = a halogen)
(a) (C2H5)2CHCl (b) (CH3)3CCl Ans. (b)
(c) (CH3)2CHCl (d) CH3Cl Sol. SN 2 reactivity
Ans. (d)
0 0
1 alkyl halide > 2 alkyl halide > 3 alkyl halide.
Sol. Less hindranced undergo more SN 2 substitution
Example-21
Example-18
In a nucleophilic substitution reaction:
The decreasing order of nucleophilicity among the
R  Br  Cl 
 R  Cl  Br  ,
DMF
nucleophiles

(A) Which one of the following undergoes complete inversion

of configuration ?
(a) C6H5CHC6H5Br (b) C6H5CH2Br
(B) (c) C6H5CH2CH3Br (d) C6H5CCH3C6H5Br
Ans. (b)
(C)
Sol. In compound B , bromine attached to benzylic bromide
give S N 2 mechanism, so inversion occure.
(D)
Example-22

Draw the stereochemical structures of the products in the

(a) (C), (B), (A), (D) (b) (B), (C), (A), (D) following reactions
(c) (D), (C), (B), (A) (d) (A), (B), (C), (D)
Ans. (b)
Sol. More concentrated vs charge more will be nucleophilicity
in A, C, D charge is delocalized by resonance (B) comes
first and most stablised by resonance is (D) comes last.

Example-19
Sol.
Tertiary alkyl halides are practically inert to substitution by
SN2 mechanism because of
(a) steric hindrance (b) inductive effect
Example-23
(c) instability (d) insolubility
Ans. (a) Following reaction
Sol. 30 alkyl halide do not undergo SN 2 mechanism due to (CH3)3CBr + H2O  (CH3)3COH + HBr is an example of
steric hindrance. (a) elimination reaction
(b) free radical substitution
Example-20
(c) nucleophilic substitution
Which of the following is the correct order of decreasing (d) electrophilic substitution
SN2 reactivity ?
Ans. (c)
(a) RCH2X > R3C X > R2CH X
Sol. It is simply nucleophilic substitution Reaction
(b) R CH2X > R2CHX > R3C X
ALKYL AND ARYL HALIDES 192

Example-24
Sol.

The alkene formed as a major product in the above elimination Example-27

reaction is
n-propyl bromide on treatment with ethanolic potassium
(a) (b) CH2=CH2 hydroxide produces
(a) propane (b) propene
(c) propyne (d) propanol
(c) (d) Ans. (b)

Sol. An alkyl halide containing at least one β - H, on treatment

Ans. (b)
with ethanoic KOH, undergoes dehydrohalogenation,
giving alkene.
Sol.
CH 3  CH 2  CH 2  Br  KOH

Ethanol
  CH 3  CH  CH 2
Example-25
Example-28
Trans-2-phenyl-1-bromocyclopentane on reaction with
1-chlorobutane on reaction with alcoholic potash gives
alcoholic KOH produces
(a) 4-phenylcyclopentene (b) 2-phenylcyclopentene
(a) but-1-ene (b) 1-butanol
(c) 1-phenylcyclopentene (d) 3-phenylcyclopentene
(c) but-2-ene (d) 2-butanol
Ans. (d)
Ans. (a)
C2 H 5OH
Sol. CH 3  CH 2  CH 2  CH 2  Cl  KOH  

Sol. CH 3CH 2  CH  CH 2
1 butene

Example-29
Example-26
Elimination of bromine from 2-bromobutane results in the Chlorination of toluene in the presence of light and heat
formation of followed by treatment with aqueous NaOH gives

(a) predominantly 2-butyne (a) o-cresol

(b) predominantly 1-butene (b) p-cresol

(c) predominantly 2-butene (c) 2, 4-dihydroxy toluene

(d) equimolar mixture of 1 and 2-butene (d) benzoic acid

Ans. (c) Ans. (d)

ALKYL AND ARYL HALIDES 193

 +  +
Sol. C H 3 M gX  CH 3C  C  H  CH 4  CH 3C  C MgX

Grignard reagent behave as a base

Sol. Example-33

(CH3)3CMg Cl on reaction with D2O produces

(a) (CH3)3CD (b) (CH3)3COD
(c) (CD)3CD (d) (CD)3COD
Ans. (a)
Sol.

Example-30 CH3 CH3

|   |
 D2O
CH 3  C  Mg Cl 
 CH 3  C  D
Identify the major product in the following reaction | |
CH3 CH3
Example-34

Alkyl halides react with dialkyl copper reagents to give

(a) alkenyl halides (b) alkanes
Sol.
(c) alkyl copper halides (d) alkenes
Ans. (b)

Example-31 Sol. R ' 2 C u L i+ R ' X  R -R '+ C u R + L iX

Each of the following reactions gives two products. Write Example-35

the structures of the products
How will you prepare m-bromoiodobenzene from benzene
Alc.KOH, heat
(i) C6H5CH2CHClC6H5   (in not more than 5-7 steps) ?
Sol. m-bromoiodobenzene can be prepared from benzene in the
HI  excess  following way-
(ii) (CH3)2CH––OCH3 
heat
1. Treating benzene with nitrating mixture which gives
Sol. nitrobenzene-

(i) C6 H 6 + HNO3 H 2SO 4 ----------> C 6 H 5 NO 2

2. Bromination of nitrobenzene,giving
HI
(ii) (CH3 )2 CH -OCH3  m-bromonitrobenzene-
C6 H5 NO2 + Br2 Fe ---------> Br  C6 H 4 NO 2
(CH3 )2 CH - I + H 2 O + CH 3 I
3. Reducing the above compound with Sn HCl-
Example-32
Br-C6 H 4 NO2 + Sn HCl ----------> Br-C6 H 4 NH 2
The treatment of CH3MgX with produces
4. Treating 3- bromoaniline with NaNO2 HCl-
(a) (b)
Br-C6 H 4 NH 2 + NaNO 2 HCl--------> Br-C6 H 4 N 2 Cl

5. Finally treating the above diazonium compound with KI ,

(c) (d)
yields m-bromoiodobenzene
Ans. (d) Br-C6 H 4 N 2 Cl + KI---------> Br-C6 H 4 I
ALKYL AND ARYL HALIDES 194

Example-36
(ii)
Write down the reaction involved in the preparation of
following using the reagents indicated against in Example-39
parenthesis.
“Ethyl benzene from benzene.” Aryl halides are less reactive than alkyl halides towards
nucleophilic reagents. Give reason.
[C2H5OH, PCl5, anhyd. AlCl3]

Sol. (i) C2 H 5 OH  PCl5  C2 H 5Cl Sol. Because of sp2 hybridized carbon the bond between carbon
and halogen is stronger. Also in conjugated systems back-
bonding by halogens lead to formation of partial double
bond character.
(ii)
Example-40

Example-37 Optically active 2-iodobutane on treatment with NaI in

acetone gives a product which does not show optical
Arrange the following in order of their activity. Explain briefly.
(i) Increasing basicity Sol. Formation of a racemic mixture.
– –
H2O, OH , CH3OH, CH3O Example-41
(ii) Increasing reactivity in nucleophilic substitution
reactions Complete the following, giving the structures of the principal
organic products
CH3F, CH3I, CH3Br, CH3Cl
Sol. Acidity order :

 
(i) CH 3OH  H 2 O  CH 3 O  O H
 
O H  CH 3 O  H 2 O  CH 3OH Sol.

Basicity order
Example-42
ii CH3 F < CH3Cl < CH3 Br < CH3 I
(ii)
Conversion of benzene diazonium chloride to chloro
Example-38 benzene is an example of which of the following reactions?
(a) Claisen (b) Friedel-craft
Write the structure of the major organic product expected
from each of the following reactions (c) Sandmeyer (d) Wurtz
Ans. (c)
(i) (CH 3 )2 C  CH 2  CH 3 
Alc.KOH

|
Cl

Sol.
(ii)

Sol.
This is sandmeyer reaction

(i)
ALKYL AND ARYL HALIDES 195

Example-43
Sol. 2CH3  CCl3 
6Ag

 CH3  CH  CH  CH3  6AgCl
Chlorobenzene can be prepared by reacting aniline with
(a) hydrochloric acid
Example-45
(b) cuprous chloride
(c) chlorine in presence of anhydrous aluminium chloride The compound formed on heating chlorobenzene with
(d) nitrous acid followed by heating with cuprous chloride chloral in the presence of concentrated sulphuric acid is

Ans. (d) (a) gammexane (b) DDT

Sol. (c) freon (d) hexachloroethane

Ans. (b)

Sol.

Example-44

The major organic compound formed by the reaction of

1, 1, 1– trichloroethane with silver powder is :
(a) Ethene (b) 2-Butyne
(c) 2-Butene (d) Acetylene
Ans. (b)
ALKYL AND ARYL HALIDES 196

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

halide, R2CuLi is prepared and then this is reacted
Introduction and Characteristic reactions of Alkyl with another alkyl halide.
Halide (b) The reagent R2CuLi can be prepared from 1°, 2° or 3°
1. alkyl halide as well as from halobenzenes
(c) both (a) and (b)
(d) none of these
7. Which of the following combinations of reactants is better
Among these compounds, which one has shortest C—Cl for making propane ?
bond ?
(a) (CH 3 )2 CuLi  CH 3CH 2 Br 
 CH 3CH 2 CH3
(a) I (b) II
(c) III (d) IV (b) Et 2 CuLi  CH 3  Br 
 CH 3  CH 2  CH 3
2. Which of the following is a primary halide (c) both of these
(a) Isopropyl iodide (b) Secondary butyl iodide (d) none of these
(c) Tertiary butyl bromide (d) Neo hexyl chloride 8. Which of the following combinations of reactants is better
3. The two optical isomers given below, namely for making neopentane ?

CH3 CH3
H Cl H Cl (a)
Cl H H Cl
C2H5 C2H5

(a) enantiomers
(b)
(b) geometrical isomers
(c) structural isomers
(c) both (a) and (b)
(d) diastereomers
(d) none of these
4. Which of the following species is an electrophile ?
Types of Solvents and Nucleophiles
(a) H (b) H
9. Which of the following compounds is not suitable solvent
(c) both (a) and (b) (d) none of these for Grignard reagent ?
5. The less reactivity of chlorine atom in CH 2 =CH-Cl is
due to
(a) Inductive effect (a) (b)

(b) Resonance stabilization

(c) Electromeric effect
(d) Electronegativity
(c) (d)
6. Corey-House synthesis is a much more convenient method
for making alkanes for which of the following reasons ?
(a) Two different alkyl halides can be used. From one alkyl
ALKYL AND ARYL HALIDES 197
10. Which of the following species is a nucleophile ? Θ Θ Θ Θ
16. F,Cl,Br, I Among these nucleophiles, which of the

(a) H2O (b) H 3 O
following orders is correct for their nucleophilicity order
(c) both (a) and (b) (d) none of these in water ?
11. Which of the following species is a nucleophile ? Θ Θ Θ Θ Θ Θ Θ Θ
(a) F>Cl >Br> I (b) I >Br >Cl>F

(a) C H 2 O (b) CH3OH
Θ Θ Θ Θ
(c) both (a) and (b) (d) none of these (c) I >Br >F>Cl (d) none of these
12. The addition of the Grignard reagent, CH 3MgBr to 17. For the following :
acetaldehyde is a nucleophilic addition to the carbonyl
group. The nucleophile in this reaction is (1) I– (2) Cl– (3) Br–

(a) CH3CHO (b) CH3 the increasing order of nucleophilicity in polar protic
solvent would be
(c) Br (d) CH3 (a) I–< Br–< Cl– (b) Cl–< Br–< I–
13. Among these nucleophiles, which of the following orders
is correct for their nucleophilicity order in gas phase ? (c) I–< Cl–< Br– (d) Br–< Cl–< I–

Nucleophilic Substitution Reaction

CH 3 , NH 2 , OH  ,F -
18. R-X+NaOH  ROH+NaX
(a) CH 3 >NH 2 >OH  >F -
The above reaction is classified as
(b) F   OH   NH 2  CH 3 (a) Nucleophilic substitution
(c) OH  >NH 2 >F - >CH 3 (b) Electrophilic substitution

(d) none of these (c) Reduction

(d) Oxidation
Θ Θ Θ Θ
14. C H 3 , N H 2 , O H, F

Among these nucleophiles, which of the following orders

is correct for their nucleophilicity in acetone ? 19.
Θ Θ Θ Θ
(a) C H 3  N H 2  O H> F
This reaction would follow which of the following
pathways predominantly?
(b) F  OH   NH 2  CH 3
(a) SN1/E1 (b) SN2/E2
Θ Θ Θ Θ
(c) O H> N H 2  F  C H 3 (c) SN1/E2 (d)SN2/E1
(d) none of these -
20. DMF
CH 3 -CH 2 -CH 2 -CH 2 -Br+ CH 3 -CH 2 -O  
Θ  Θ Θ
15. F, Cl , Br, I This reaction would follow which of the following pathway
Among these nucleophiles, which of the following orders predominantly?
is correct for their nucleophilicity order in DMF ? (a) SN1 (b) SN2
Θ  Θ Θ Θ Θ Θ Θ
(c) E1 (d) E2
(a) F> Cl >Br > I (b) I >Br > Cl >F

Θ Θ Θ Θ
(c) I >Br >F>Cl (d) none of these
ALKYL AND ARYL HALIDES 198
 27. What will be the increasing order towards SN1 reaction for
21. CH3 – CH 2 – CH 2  Br  I 
DMSO  the following:
This reaction would follow which of the following pathway
predominantly?
(a) SN1 (b) SN2
(c) E1 (d) E2
22. Which one of the following is most reactive towards
nucleophilic substitution ?

(a) H 2 C=CH-Cl (b) C6 H 5Cl (a) P > Q > R > S (b) Q > R > S > P
(c) Q > P > R > S (d) Q > R > P > S
(c) CH 3 -CH=CH-Cl (d) ClCH 2 -CH=CH 2
28. Which of the following is the incorrect statement regarding
23. Which of the following two reactions would be faster? the following four alkyl halides?
Θ Θ
(a) CH 3 -I+ O H  CH 3 -OH+ I

Θ Θ
(b) CH 3 -Cl+ OH  CH 3 -OH+ Cl

(c) both have similar rates

(d) rates cannot be predicted
Θ 
24. H 3 C-S Na +CH 3 CH 2 -X 
(a) I is most reactive for a SN2 reaction
The reaction is fastest when X is: (b) IV is most reactive for E1 reaction
(a) – OH (b) – F (c) II is more reactive than III in SN1 reaction
(d) IV is most reactive for E2 reaction
O O
|| || 29. When the concentration of alkyl halide is tripled and
(c) O  C  CF3 (d) O  C  CH 3
Θ
concentration of O H is reduced to half, the rate of SN2
25. Arrange the following halides in the decreasing order of
reaction increased by:
SN1 reactivity
(a) 3 times (b) 1.5 times
(I) CH3CH2CH2Cl
(c) 2 times (d) 6 times
(II)CH2=CHCH(Cl)CH3 30. Increasing order of SN1 reaction will be
(III) CH3CH2CH(Cl)CH3
(P) (Q)
(a) I > II > III (b) II > III > I
(R) H 3 C-Br (S) H 2 C=CH-Br
(c) II > I > III (d) III > II > I
26. Arrange the following in decreasing order of reactivity (a) S > P > Q > R (b) Q > S > R > P
towards SN1 reaction (c) Q > R > P > S (d) R > Q > P > S
31. Predict the major product of the reaction
(P) C H 3 -C l (Q)

(R) (S) (a) (b)

(a) S > R > Q > P (b) S > Q > R > P

(c) R > S > Q > P (d) P > Q > R > S
(c) (d)
ALKYL AND ARYL HALIDES 199
32. SN1 competes with E1 and SN2 competes with E2. This is 37. In SN1 reaction, the racemization takes place. It is due to
because
(a) conversion of configuration
(a) both SN1 and E1 have same rate-determining-step. (b) retention of configuration
Therefore E1 competes with SN1.
(c) inversion of configuration
(b) a base is a nucleophile and a nucleophile is a base,
(d) both (b) & (c)
Therefore, SN2 competes with E2.
38. The increasing order of reactivity of the following bromides
(c) both a and b in SN1 reaction is
(d) none of these
33. Arrange the following in decreasing order of SN2 reaction
(P) CH3Cl
(Q) CH3CH2Cl
(R) CH3CH2CH2Cl
Cl

(S)
CH 3  CH  CH 3
(a) P > Q > S > R (b) P > Q > R > S
(c) S > R > Q > P (d) S >Q> R > P
(a) III > I > II > IV
(b) III > II > I > IV
34.
(c) II > III > I > IV
(d) II > I > IV > III
39. Arrange the following halides in decreasing order of
reactivity in SN1 reaction
Arrange the following in decreasing order of SN2 reaction
(a) P > Q > R > S (b) R > P > Q > S
(c) Q > R > P > S (d) R > Q > P > S
35. Isopropyl chloride undergoes hydrolysis by : (I) (II)
(a) SN1 mechanism
(b) SN2 mechanism
(c) SN1 or SN2 mechanism
(d) Neither SN1 nor SN2 mechanism
36. Among the following, the one which reacts most readily (III) (IV)
with ethanol is
(a) p-nitrobenzyl bromide
(b) p-chlorobenzyl bromide (a) II > III > IV > I

(c) p-methoxybenzyl bromide (b) IV > III > II > I

(d) p-methylbenzyl bromide (c) III > IV > II > I

(d) I > II > III > IV
ALKYL AND ARYL HALIDES 200
40. Rate of SN1 reaction is: The order of fastest SN1 reaction will be
(a) S > P > Q > R (b) R > Q > P > S
(P) (c) Q > R > P > S (d) S > Q > P > R

(Q)
43.

(R) The decreasing order of SN1 reaction will be

(a) P > Q > R > S (b) S > P > Q > R
(c) R > Q > P > S (d) R > P > Q > S
(S) 44. Which of the following is the example of SN2 reaction

(a) S > Q > R > P (b) S > R > P > Q (a) CH 3 Br+OH -  CH 3 OH+Br -

(c) P > Q > R > S (d) S > R > Q > P Θ Θ

(b) CH 3  CH(Br)-CH 3 +O H  CH 3CH(OH)-CH 3 + Br

-H 2 O
(c) CH3 CH 2 OH   CH 2 =CH 2

41.

(d)

45.

The correct order of stability of the above compounds is

(a) S > R > Q > P (b) R > S > Q > P
(c) Q > R > S > P (d) P > Q > R > S

42. Arrange the following in the deceasing order of their rate

of Nucleophilic substitution.
(a) Q > R > P > S
(b) R > Q > S > P
(c) P > Q > R > S
(d) S > P > R > Q
ALKYL AND ARYL HALIDES 201

(c) Both (a) and (b)

(d) Neither (a) nor (b)

46. 49. The rate of SN1 reaction is fastest with:

(a) CH CH3

Br

(b) CH2 Br

Arrange the following in the decreasing order of SN2

reaction:
(a) P > R > S > Q (b) P > Q > R > S
(c) P > R > Q > S (d) R > Q > S > P (c) CH NO2

47. Iodine from iodoethane can be substituted by cyanide Br

group in a number of ways. Which of the following is true
statement ?
(a) With either KCN or AgCN, EtCN is formed as major
product. (d)
(b) With either KCN or AgCN, EtNC is formed as major
product. Elimination Reaction
(c) With AgCN, EtCN and with KCN, EtNC is formed.
(d) With AgCN, EtNC while with KCN, EtCN is formed as
major product. 50.
48. What is the product of the following reaction ?
This reaction would follow which of the following pathway
predominantly?
(a) SN1 (b) SN2
(c) E1 (d)E2
51. What alkyl halide would give the following alkene as the
only product in an elimination reaction

(a)

(a) (b)

(b)

(c) (d) Both (a) and (b)

ALKYL AND ARYL HALIDES 202

57. An halide C5H11Br on treatment with alc. KOH give

2-pentene only. The halide will be:
(a)
52.

The major product obtained when this substrate is (b)

subjected to E1 reaction will
(c)

(a) (b)

(d)

(c) (d) none of these

58.
53. 2-bromopentane is heated with potassium ethoxide in
ethanol. The major product obtained is
(a) Pent-1-ene (b) cis pent-2-ene The major product obtained when this alkyl halide is
(c) trans pent-2-ene (d) 2-ethoxypentane subjected to E2 – reaction will be
54. n-Propyl bromide on treatment with ethanolic potassium
hydroxide produces (a)
(a) Propane (b) Propene
(c) Propyne (d) Propanol
(b)

55.

In the above reaction, maximum Saytzeff product will be (c)

obtained where X is:
(a) I (b) Cl
(c) Br (d)F
56. Find the major product of the reaction: (d) All three products in equal proportions

(a) (b)

(c) (d) Both (a) and (b)

ALKYL AND ARYL HALIDES 203

59. (a)

The major product obtained when this alkyl halide is

subjected to E2 reaction under the treatment of potassium
(b)
tert-butoxide will be

(a)

(c)
(b)

(d) all three in equal proportions

(c) both (a) and (b) 63. If tert-butyl bromide and NaNH2 reacts, the product formed
(d) none of these is
(a) tert-butylamine
(b) tert-butylammonium bromide
(c) a mixture of butyl amines
60. (d) iso butylenes
64. The major product obtained on treatment of
Which of the following products will be major if this CH3CH2CH(F)CH3 with CH3O–/ CH3OH is
substrate is subjected to E2 reaction?
(a) CH3CH2CH(OCH3) CH3
(b) CH3CH=CHCH3
(a) (b) (c) CH3CH2CH=CH2
(d) CH3CH2CH2CH2OCH3
(c) both in equal proportion
65. Major product of the following reaction is:
(d) not predictable

61.

The products obtained when this substrate is subjected

to E2 reaction will be

(a) (b)
(a) (b)

(c) (d) all of these

(c) (d)

62.

The major product obtained when this alkyl halide is

subjected to E2 reaction will be
ALKYL AND ARYL HALIDES 204

66.
(c) (d)

The major alkene obtained when this alkyl halide is

70. Which of the following will undergo fastest elimination
subjected to E1 reaction will be
with alcoholic KOH?

(a) (b)
(a) (b)

(c) (d) All in equal proportions

(c) (d)
67. Find the major product of the following reaction

71.

(a) (b)

(a) (b)
(c) (d)

68. The major product formed in the following reaction is

(c) (d) No reaction

72.
(a) (b)

(a) (b)

(c) (d)

(c) (d)
69. In the above reaction Hoffman product is major when base
is:

(a) (b)
ALKYL AND ARYL HALIDES 205

This reaction would follow which of the following pathway

73. predominantly?
(a) SN1 (b) SN2
(c) SN1/E1 (d) SN2/E2
The major product obtained when this alkyl halide is
77. Choose the correct major product of the reaction:
subjected to E2 reaction will be
(a)

(b)
(a) (b)

(c)

(d) all in equal proportion (c) (d)

74. 78.

The major product obtained when this substrate is

subjected to E2 reaction will be (a) (b)

(a) (b) (c) (d)

(c) (d) none of these

79.
CH3
|
75. CH 3  CH 2  CH 2 Br   CH 3  C  O 
DMSO

|
CH3
This reaction would follow which of the following pathway
(a) (b)
predominantly?
(a) SN1 (b) SN2
(c) E1 (d) E2

(c) (d)
76.
ALKYL AND ARYL HALIDES 206
80. What is the major product of the reaction sequence?

83.

(a) (b)

(a) (b)
(c) (d)

81. The product B of the following sequence, would be

(c) (d)
CH3I
Ag2O heat

 
OH 2   B

84.

I II Identify the major product Y:

III IV (a) (b)

V (c) (d)

(a) I (b) II Physical and Chemical Properties of Alkyl Halides

(c) III (d) IV and V 85. Correct order of boiling point for the alkyl halide is
(a) C2H5Cl > C2H5Br > C2H5I

82. When CH3CH2CHCl2 is treated with NaNH2 the product (b) C2H5I > C2H5Br > C2H5Cl
formed is (c) C2H5I > C2H5Cl > C2H5Br

(a) CH 3  CH  CH 2 (d) C2H5Br > C2H5I > C2H5Cl

86. Ethyl bromide reacts with silver nitrite to form
(b) CH 3  C  CH
(a) Nitroethane
(c) CH3 CH2 CH  NH 2  Cl  (b) Nitroethane and ethyl nitrite
(c) Ethyl nitrite
(d) CH3 CH 2 CH  NH 2 2 (d) Ethane
ALKYL AND ARYL HALIDES 207
Aq.KCN P should be
87. CH3 – CH2 – CH2 – I 
EtOH
 P
 Major 
P should be (a) (b)
(a) CH3 – CH2 – CH2 – CN
(c) both of these in equal proportions
(b) CH3 – CH = CH2
(d) none of these
(c) both (a) and (b) in equal proportions
92. An alkyl bromide (X) reacts with Na to form 4,
(d) none of these
5-diethyloctane. Compound X is
88. Alkyl halides react with Mg in dry ether to form
(a) CH 3 (CH 2 )3 Br
(a) Magnesium halide (b) Grignard’s reagent
(c) Alkene (d) Alkyne (b) CH3(CH2)5 Br

89. What is the major product of the reaction ? (c) CH3(CH2)3CH.Br.CH3

(d) CH3(CH2)2CH.Br.CH2CH3
Na
93. CH3 – CH2 – CH2 – Br + CH3 – CH2 – Br  P
ether
P is :
(a) P is mixture of three alkanes (n–hexane, n–butane and
n–pentane); none is formed in good yield
(a) (b) P is a mixture of only two alkanes (n–hexane and n–
butane); both are formed in good yield.
(c) both (a) and (b) depending upon other conditions
(b)
(d) none of these
94. Vinyl chloride reacts with HCl to form
(c) (a) 1, 1- dichloro ethane
(b) 1, 2- dichloro ethane
(c) Tetrachloro ethylene
(d)
(d) Mixture of 1, 2 and 1, 1 – dichloro ethane

90. Which of the following reactions is a good way to prepare 95. In the following reaction find the correct product :
methyl tert–butyl ether ?

(a) CH3O–Na+ + (CH3)3 CBr 



(b) (CH3)3CO– K+ + CH3I 



NaOH
(c) (CH3)3COH + CH3OH  
(a) (b)
(d) CH3MgBr + (CH3)3COCl 


91.
(c) (d)
ALKYL AND ARYL HALIDES 208
96. Ethylene dichloride and ethylidene chloride are isomeric
compounds. The false statement about these isomers is
100. In the following sequence of reactions
that they
(a) React with alcoholic potash and give the same product
(b) Are position isomers The product (C) is
(c) Contain the same percentage of chlorine (a) Propan – 2 – ol (b) Propan – l – ol
(d) Are both hydrolysed to the same product (c) Propyne (d) Propene
101. What is the major product of the reaction sequence ?
97. CH 3  CH 2  NH 2  CH 3  I 
 P
 Excess   Major 
P should be
(a) CH3 – CH2 – NH – CH3
(a) (b)

(b)
(c) (d)
(c)
(d) CH2 = CH2 Chemical Reactions of Aryl Halides
102. C6H5Cl prepared by aniline with

KCN (a) HCl

98. 
H O/ EtOH
 P
2  Major  (b) Cu2Cl2
(c) Cl2 in presence of anhydrous AlCl3
(d) HNO2 and then heated with Cu2Cl2

(a) 103. In addition-elimination pathway of nucleophilic aromatic

substitutions, which of the following compounds is most
reactive ?

(b)
(a) (b)
(c) both (a) and (b) in equal proportions
(d) None of these

Na / Ether
A (C6H13Br) 
99.  4, 5–diethyloctane
Deduce the structure of ‘A’ :
(c) (d)
(a) (b)

(c) (d)
ALKYL AND ARYL HALIDES 209

104. In addition-elimination pathway of nucleophilic aromatic 108. Bottles containing C6H5I and C6H5CH2I lost their original
substitutions, which of the following compounds is most labels. They were labelled A and B for testing. A and B
reactive ? were separately taken in test tubes and boiled with NaOH
solution. The end solution in each tube was made acidic
with dilute HNO3 and then some AgNO3 solution was
added. Substance B give a yellow precipitate. Which one
(a) (b) of the following statements is true for this experiment
(a) A was C6H5I
(b) A was C6H5CH2I
(c) B was C6H5I
(d) Addition of HNO3 was unnecessary

(c) (d) 109.

To make this ether which of the following reactions will be

105. In addition elimination pathway of nucleophilic aromatic most suitable ?
substitutions, a–NO2 groups is
(a) o, p–directing and activating
(a)
(b) o, p–directing and deactivating
(c) m–directing and activating
(d) m–directing and deactivating
(b)
106. Which of the following has the fastest rate of the reaction
with NaOC2H5 ?
(a) p–fluoronitrobenzene (b) p–bromonitrobenzene
(c) p–chloronitrobenzene (d) p–iodonitrobenzene (c)
107. Which of the following reaction is called Wurtz-Fittig
reaction ? (d) both (b) and (c)
110. The following transformation proceeds through
(a)

(b)

(a) benzyne intermediate

(c) (b) oxirane
(c) electrophilic - addition
(d) both (b) and (c) (d) nucleophilic aromatic substitution
ALKYL AND ARYL HALIDES 210
(c) Halide exchange
(d) Direct halogenation of alkanes
115. The following reaction is known as
111.

This reaction follows (a) Kharasch effect

(a) SN 1 pathway (b) Darzen’s process

(c) Williamson’s synthesis
(b) SN 2 pathway
(d) Hunsdiecker synthesis reaction
(c) addition-elimination pathway 116. Which of the following reagents could be used to convert
(d) none of these cyclohexanol to chlorocyclohexane ?
(a) Cl2, light (b) SOCl2
(c) PBr3 (d) none of these
1. HO /  117. Decreasing order of reactivity of HX in the reaction
112. 
  P
2. H  Major  ROH + HX  RX + H2O
(a) HI > HBr > HCl > HF
(b) HBr > HCl > HI > HF
Based on the above reaction, the major product would be
(c) HCl > HBr > HI > HF
(d) HF > HBr > HCl > HI

118. C3H8 + Cl2 C3H7Cl + HCl is an example of which of

the following types of reactions
(a)
(a) Substitution (b) Elimination
(c) Addition (d) Rearrangement
119. obtained by chlorination of n-

butane will be :

(b) (a) meso form (b) racemic mixture

(c) d-form (d) l-form
120. Which of the following organic compounds will give a
(c) both in equal proportions mixture of 1-chlorobutane and 2-chlorobutane on
(d) none of these hydrochlorination (HCl)
Preparation of Alkyl Halides (a)

113. Silver acetate + Br2 The main product of this

reaction is
(a) CH3 — Br (b) CH3COI (b)
(c) CH3COOH (d) None of these (c)
114. Preparation of alkyl halides in laboratory is least preferred (d)
by
(a) Treatment of alcohols
(b) Addition of hydrogen halides to alkenes
ALKYL AND ARYL HALIDES 211

CH2 CH2 + HBr

Peroxide
(A) 124. What will be the product in the following reaction
121.

(A) is :

(a) CH3 CH2Br

Br

(b) CH3 CH3 (a) (b)

Br Br
Br Br

(c) CH3 (c) (d)

CH3

(d) BrCH2 CH2Br

125. Analyse the following reaction and identify the nature of
A and B
122. Consider the following sequence of reaction

CH CH MgBr
3 2 3 PBr
  A  B
HO 3
The product B is :

(a)
(a) (b)

(c) (d) (b)

Preparation of Aryl Halides

123.
(c)

In the above process product A is

(d)
(a) Fluorobenzene (b) Benzene
(c) 1, 4-difluorobenzene (d) 1, 3-difluorobenzene
ALKYL AND ARYL HALIDES 212
129. Which of the following is an anaesthetic
(a) C 2 H 4 (b) CHCl 3
NBS KCN (c) CH 3 Cl (d) C 2 H 5 OH
126. 
(2Mole)
 A  B;
1Mole
130. Chloroform for anesthetic purposes is tested for its
purity with the reagent
(a) Silver nitrate
Product B is :
(b) Lead nitrate
(c) Ammoniacal Cu2Cl2
(d) Lead nitrate
131. Chloropicrin is obtained by the reaction of
(a) (b)
(a) Chlorine on picric acid (b) Nitric acid on chloroform
(c) Steam on carbon tetrachloride
(d) Nitric acid on chlorobenzene
132. Statement “Ozone in atmosphere is decreased by chloro-
fluoro-carbon (Cl 2 F2 C)

(c) (d) (a) Is true

(b) Is false
(c) Only in presence of CO 2
127. Consider the following reactions, (d) Only in absence of CO2
133. The formula of freon-12 is :
(a) CClF3 (b) CH2Cl2
(c) CCl2F2 (d) CH2F2
134. Haloforms are trihalogen derivatives of
(a) Ethane (b) Methane
(c) Propane (d) Benzene
The end product ‘S’ is :
135. CCl4 cannot give precipitate with AgNO3 due to
(a) Formation of complex with AgNO3
(b) Evolution of Cl2 gas
(a) (b) (c) Chloride ion is not formed
(d) AgNO3 does not give silver ion
136. An important insecticide is obtained by the action of chloral
on chlorobenzene. It is
(a) BHC (b) Gammexene
(c) (d) (c) DDT (d) Lindane
137. DDT is prepared by reacting chlorobenzene with
(a) CCl4 (b) CCl3 –– CHO
Polyhalogen Compounds (c) CHCl3 (d) Ethane
128. Iodoform can be used as
(a) Anaesthetic (b) Antiseptic
(c) Analgesic (d) Antifebrin
ALKYL AND ARYL HALIDES 213
138. Which of the following cannot be obtained as the only 147. How many of the following can give ppt. of
product in the Wurtz’s coupling reaction of halides with
sodium metal in ether solution ? AgCl with both aq. AgNO3 and alc. AgNO3.

(a) (b)

148. How many of the following reaction product formation

(c) (d) all of these. takes place by Hoffmann’s rule?
139. A sample of chloroform being used as anaesthetic is tested
by
(a) Fehling solution
(b) Ammonical Cu2Cl2
(c) AgNO3 solution
(d) None of these.
Numerical Type Questions
140. How many isomers are possible with trisubstituted
benzene with all the three groups same ?
141. How many of the following statements are correct?

(i) The C–Cl bond in chlorobenzene is shorter than in

chloroethane.

(ii) The C–Cl bond in chlorobenzene has some double 149. 2, 6 - Dimethylheptane on monochlorination produces…….
bond character. derivatives
(iii) It is difficult to replace chlorine from chlorobenzene 150. How many of the following reactions are
than from benzoyl chloride. correct?
(iv) Chlorobenzene on further chlorination gives (i) CH3CH = CH2 + HCl  CH3CHClCH3
m-dichlorobenzene. (ii) CH3CH = CH2 + HBr  CH3CH2CH2Br
142. The fittig reaction involves x number of aryl Peroxide
(iii) CH3CH = CH2 + HBr 
halide molecules x is
CH3CH2CH2Br
143. Number of –bonds present in B.H.C. (Benzene
Peroxide
(iv) CH3CH = CH2 + HI  CH3CHICH3
hexachloride) are
144. In CH3CH2Br, % of Br is
145. Number of stereoisomers of the compound, 2-chloro-4-
methylhex-2-ene is
146. The number of enantiomers of the compound
CH3CHBrCHBrCOOH is
ALKYL AND ARYL HALIDES 214

EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS

1. 2-chloro-2-methylpentane on reaction with sodium 4. The gas evolved on heating CH3MgBr in methanol is :
methoxide in methanol yields: (2016)
Online 2016 SET (1)
(a) HBr (b) Methane
(c) Ethane (d) Propane
(a) 5. Bromination of cyclohexene under conditions given
below yields : Online 2016 SET (2)

(b)

(c)

(a) (a) and (c) (b) (c) only (a) (b)

(c) (a) and (b) (d) All of these
2. The product of the reaction given below is: (2016)

(c) (d)

6. Which one of the following reagents is not suitable for

(a) (b)
the elimination reaction ? Online 2016 SET (2)

(a) NaOH/H2O
(c) (d) (b) NaOEt/EtOH
(c) NaOH/H2O - EtOH
(d) NaI
3. The reaction of propene with HOCl (Cl2 + H2O) proceeds 7. Fluorination of an aromatic ring is easily accomplished
through the intermediate : (2016) by treating a diazonium salt with HBF4 . Which of the

(a) CH3  CH  CH2  Cl following conditions is correct about this reaction?
Online 2016 SET (2)
(b) CH3  CH(OH)  CH2
(a) Only heat
(c) CH3  CHCl  CH2 (b) NaNO2/Cu
(c) CuO2/H2O
(d) CH3  CH  CH2  OH
(d) NaF/Cu
ALKYL AND ARYL HALIDES 215

8. Which of the following compounds will not undergo 11. The increasing order of reactivity of the following halides
Friedel Craft’s reaction with benzene ? for the SN1 reaction is (2017)
Online 2017 SET (1) (I) CH3CH(Cl)CH2CH3
(II) CH3CH2CH2Cl
(a) (b) (III) p-H3CO–C6H4 – CH2Cl
(a) (III) < (II) < (I) (b) (II) < (I) < (III)
(c) (I) < (III) < (II) (d) (II) < (III) < (I)
12. The major product of the following reaction is :
(c) (d)
(2018)

9. The major product of the following reaction is :

KOH,CH3 OH
CH3CHCH 2CHCH 2 CH3 
heat

| |
Br Br
Online 2017 SET (1)
(a) CH2 = CHCH2CH = CHCH3
(a) (b)
(b) CH2 = CHCH = CHCH2CH3
(c) CH3CH = C = CHCH2CH3
(d) CH3CH = CH – CH = CHCH3
10. The major product of the following reaction is (c) (d)
Online 2017 SET (2)
13. Which of the following will most readily give the
dehydrohalogenation product.
Online 2018 SET (1)

(a) (b)

(a) (b)
(c) (d)

14. The total number of optically active compounds formed

in the following reaction is : Online 2018 SET (2)

(c) (d)

(a) Two (b) Four

(c) Six (d) Zero
ALKYL AND ARYL HALIDES 216
15. The major product of the following reaction is :
Online 2019 SET (2)
(a) (b)

(c) (d)
(a) (b)
19. The major product of the following reaction is :

(c) (d)

16. The major product of the following reaction is

(2019-04-10/Shift-1)
(2019-01-12/Shift-2)
(a)

(a) (b) (b)

(c) (d) (c)

17. Heating of 2-chloro-1-phenylbutane with EtOK/EtOH

gives X as the major product. Reaction of X with
Hg(OAc)2 / H 2 O followed by NaBH 4 gives Y as the
major product. Y is: (2019-04-09/Shift-2) (d)

(a) (b) 20. Which of the following compounds will show retention
in configuration on nucleophilic substitution by OH–
(c) (d) ion? (2020-09-02/Shift-1)

18. The major product of the following reaction is

(a) (b)

(2019-01-09/Shift-1) (c) (d)

ALKYL AND ARYL HALIDES 217
21. The major product obtained from E2– elimination of
3- bromo-2-fluoropentane is: (2020-09-02/Shift-2) (B) R  would be easily formed if the substituents are
bulky.
(C) The reaction is accompanied by racemization.
(a) (D) The reaction is favoured by non-polar solvents.
Which observations are correct ?

(b) (2020-09-03/Shift-1)
(a) (A) and (B) (b) (A), (B) and (C)
(c) (A) and (C) (d) (B) and (d)
24. The decreasing order of reactivity of the following
(c) compounds towards nucleophilic substitution (SN2) is :

(d)

22. Consider the reaction sequence given below :

(2020-09-03/Shift-2)
(a) (III) > (II) > (IV) > (I) (b) (IV) > (II) > (III) > (I)
(c) (II) > (III) > (IV) > (I) (d) (II) > (III) > (I) > (IV)
25. Among the following compounds, which one has the
shortest C – Cl bond? (2020-09-04/Shift-2)

(a) (b)
Which of the following statements is true :
(2020-09-02/Shift-2)
(a) Changing the concentration of base will have no
effect on reaction (1).
(c) (d)
(b) Doubling the concentration of base will double the
rate of both the reactions.
(c) Changing the base from OH– to –OR will have no 26. The increasing order of the boiling points of the major
effect on reaction (2). products A, B and C of the following reaction will be:
(d) Changing the concentration of base will have no
(1)
effect on reaction (2).
23. The mechanism of SN1 reaction is given as : (2)

(3)
(2020-09-06/Shift-2)
(a) 1 < 2 < 3 (b) 3 < 1 < 2
A student writes general characteristics based on the
(c) 1 < 3 < 2 (d) 2 <3< 1
given mechanism as :
(A) The reaction is favoured by weak nucleophiles.
ALKYL AND ARYL HALIDES 218

27. Consider the following reactions: (a) B > A > D > C (b) B >D>C>A
Conc.H2 SO 4
(a)  CH 3 3 CCH  OH  CH 3   (c) B >D>A> C (d) D>B>C>A
 
30. Which of the following reactions will not produce a
 CH3 3 C O K
(b)  CH3  CHCH  Br  CH3 
2
 racemic product? ( 2020-01-09/Shift-2)
Alc. KOH
(c)  CH3 2 CHCH  Br  CH3   (a)

 CH3 2 C  CH 2 CHO  
|
(d)
OH (b)
Which of these reaction(s) will not produce Saytzeff
product? (2020-01-7/Shift-1)
(c)
(a) b and d (b) d only
(c) a, c and d (d) d only (d)
28. For the following reactions,

31. The product formed in the first step of the reaction of

with excess Mg/Et2O(Et = C2H5) is:

(2021-02-24\Shift - 1)
ks and ke, are, respectively, the rate constants for
(a)
ks
substitution and elimination, and  
ke , the
correct option is ______. (2020-01-07/Shift-2)
(b)
(a)  A   B and ke  A   ke  B 

(b) B   A and ke  A   k e  B 
(c)
(c)  A  B and ke  B   k e  A 

(d)  B   A and ke  B   ke  A
29. The decreasing order of reactivity towards
dehydrohalogenation (E1) reaction of the following (d)
compounds is:

(A) (B)

(C) (D)

(2020-01-08/Shift-1)
ALKYL AND ARYL HALIDES 219
32. The correct order of the following compounds showing 34. Match List-I with List-II (2021-02-26/Shift-2)
increasing tendency towards nucleophilic substitution
reaction is (2021-02-24/Shift - 2)

(a) (i) < (ii) < (iii) < (iv) (b) (iv) < (i) < (ii) < (iii)
(c) (iv) < (iii) < (ii) < (i) (d) (iv) < (i) < (iii) < (ii)
33. Identify A and B in the chemical reaction.
(2021-02-25/Shift - 1)

Choose the correct answer from the options given below

(a) A – (ii), B – (i), C – (iv), D – (iii)
(b) A – (iii), B – (i), C – (iv), D – (ii)
(a)
(c) A – (iii), B – (iv), C – (i), D – (ii)
(d) A – (ii), B – (iv), C – (i), D – (iii)
35. The correct pair(s) of the ambident nucleophiles is (are):
(a) AgCN/KCN (2021-03-17/Shift - 2)

(b) (b) RCOOAg/RCOOK

(c) AgNO2/KNO2
(d) Agl/KI
(a) (B) only (b) (A) and (C) only
(c) (B) and (C) only (d) (A) only
36. The correct decreasing order of densities of the
(c) following compound is : (2021-07-25/Shift - 2)

(d) (a) (D) > (C) > (B) > (A)

(b) (C) > (D) > (A) > (B)
(c) (C) > (B) > (A) > (D)
(d) (A) > (B) > (C) > (D)
ALKYL AND ARYL HALIDES 220

37. Given below are two statements:

(2021-07-25/Shift - 2)
(c) (d)
Statement I : Chlorofluorocarbons breakdown by
radiation in the visible energy region and release chlorine
41. The gas 'A' is having very low reactivity reaches to
gas in the atmosphere which then reacts with
stratosphere. It is non–toxic and non–flammable but
stratospheric ozone.
dissociated by UV—radiations in stratosphere. The
Statement II : Atmospheric ozone reacts with nitric oxide intermediates formed initially from the gas 'A' are :
to give nitrogen and oxygen gases, which add to the
(2021-08-27/Shift - 1)
atmosphere.
   
For the above statements choose the correct answer (a) Cl O C F2 Cl (b) Cl O C H 3
from the options given below:    
(c) C H 3  C F2 Cl (d) C l  C F2 Cl
(a) Statement I is incorrect, but statement II is true
(b) Both statement I and II are false 42. In the following sequence of reactions the P is :

(c) Statement I is correct, but statement II is false (2021-08-27/Shift - 1)

(d) Both statement I and II are correct

38. Among the following compounds I-IV, which one forms
a yellow precipitate on reacting sequentially with
(i) NaOH (ii) dil. HNO3 (iii) AgNO3?
(2021-08-26/Shift - 1)
(a)

(b)
(a) II (b) IV
(c) I (d) III
(c)
39. Excess of isobutane on reaction with Br2 in presence of
light at 125 oC gives which one of the following as the
major product? (2021-08-26/Shift - 1)
(d)

(a) (b) 43. Given below are two statements :

(2021-08-27/Shift - 2)
Statement I : Ethyl pent–4–yn–oate on reaction with
(c) (d) CH3MgBr gives a 3°–alcohol.
Statement II : In this reaction one mole of ethyl
40. The structure of the starting compound P used in the pent–4–yn–oate utilizes two moles of CH3MgBr.
reaction given below is (2021-08-27/Shift - 1) In the light of the above statements, choose the most
appropriate answer from the options given below :
(a) Both Statement I and Statement II are false.
(b) Statement I is false but Statement II is true.
(c) Statement I is true but Statement II is false.
(a) (b)
(d) Both Statement I and Statement II are true.
ALKYL AND ARYL HALIDES 221

44. (2021-03-16/Shift - 2) 45.

The above reaction requires which of the following

Identify the reagent(s) 'A' and condition(s) for the reaction conditions? (2021-03-17/Shift - 1)
reaction (a) 623 K, Cu, 300 atm
(a) A = HCl ; Anhydrous AlCl3 (b) 573 K, 300 atm
(b) A = HCl, ZnCl2 (c) 573 K, Cu, 300 atm
(c) A = Cl2; dark, Anhydrous AlCl3 (d) 623 K, 300 atm
(d) A = Cl2; UV light
ALKYL AND ARYL HALIDES 222

EXERCISEEXERCISE
- 3 : ADVANCED OBJECTIVE
- 3 : ADVANCED QUESTIONS
OBJECTIVE QUESTIONS
Objective Questions I [Only One Correct Option]
(c) PhCH2CH2Cl (d)
1. C6H6Cl6, on treatment with alcoholic KOH, yields
7. What is true about the following reaction?
(a) C6H6 (b) C6H3Cl3
(c) (C6H6) OH (d) C6H6Cl4
2. Choose the major product of the reaction.

(a) Only substitution product is formed.

(b) Only elimination product is formed.

(a) (b) (c) Both substitution and elimination products are

formed and substitution dominates.
(d) Both substitution and elimination products are
(c) (d) formed and elimination dominates.
8. Which of the following bases would give the best yield
for the substitution product when reacted with 2-
3. chloropropane ?
– –
(a) CH3COO (b) OH
– –
(c) NH2 (d) CH3CH2O
This reaction would follow which of the following
pathway predominantly ? 9. Debromination of mesodibromobutane will give the
product as :
(a) SN1 (b) SN2
(a) n-butane (b) 2-butyne
(c) E1 (d) E2
(c) cis-2-butene (d) Trans-2-butene
4. Which of these do not form Grignard reagent
10. Which of the following undergoes E2 elimination in the
(a) CH3F (b) CH3Cl
presence of a strong base to yield one product ?
(c) CH3Br (d) CH3I
(a) 3-bromo-2-methylpentane
5. Which of the following statements is correct about
retention/invertion of configuration during the course (b) 1-bromo-1-methylcyclohexane
of a reaction? (c) 1-bromo-3, 3-dimethylbutane
(a) Configuration is retained if reagent attacks from the (d) 3-bromo-3-methylpentane
same side of leaving group. 11. What is the major product of the following reaction?
(b) Configuration is inverted if reagent attacks from the
backside of leaving group.
(c) No change in configuration is possible if no bonds
of the asymmetric centre are cleaved during the course
(a) (b)
of reaction.
(d) all of these
6. The compound most reactive towards SN1 reaction is (c) (d)
(a) Me3C––CH2Cl (b) MeOCH2Cl
ALKYL AND ARYL HALIDES 223
12. Choose the answer that incorrectly shows the major
product of the reaction. Br  H O
2 2 
18.  Product :
(a)

(b) (a) (b)

(c)
(c) (d)

19. When but –3-en -2- ol reacts with aq. HBr, the product
(d) formed is
13. Among the following the most reactive towards alcoholic (a) 3 - bromobut - 1- ene
KOH is
(b) 1 - bromobut - 2- ene
(a) CH2 = CHBr (b) CH3COCH2CH2Br
(c) A mixture of both a and b
(c) CH3CH2Br (d) CH3CH2CH2Br
(d) 2 - bromobut - 2 - ene
14. Which of the following represents the correct order of
densities ? Cl  H O
2 2  Major product :
20. 
(a) CCl4 > CHCl3 > CH2Cl2 > CH3Cl > H2O
(b) CCl4 > CHCl3 > CH2Cl2 > H2O > CH3Cl
(c) H2O > CH3Cl > CH2Cl2 > CHCl3 > CCl4 (a)
(d) CCl4 > CHCl3 > H2O > CH2Cl2 > CH3Cl
15. Which of the following are arranged in the decreasing
order of dipole moment ?
(b)
(a) CH3Cl, CH3Br, CH3F
(b) CH3Cl, CH3F, CH3Br
(c) CH3Br, CH3Cl, CH3F (c)
(d) CH3Br, CH3F, CH3Cl
16. The conversion of 2, 3-dibromobutane to 2-butene with
Zn and alcohol is (d)
(a) -Elimination
Cl
2 
(b) Redox reaction 21. 
CCl4
(c) Both -elimination and redox reaction
(d) -Elimination
17. The number of possible enantiomeric pairs that can be
Stereochemistry of the product are :
produced during monochlorination of 2-methyl butane
is : (a) diastereomers
(a) 3 (b) 4 (b) meso
(c) 2 (d) 1 (c) racemic mixture
(d) pure enantiomers
ALKYL AND ARYL HALIDES 224
22. A compound ‘A’ has molecular formula C5H9Cl. It does not Cl
react with bromine in CCl4. On treatment with strong base, it
produces single compound ‘B’ (C5H8) and reacts with Br2 (a) (b)
(aq). Ozonolysis of ‘B’ produces a compound C5H8O2. Br
Which of the following is structure of A ?
(c) (d)
27. Which of the following alkyl halides is not suitable for
(a) (b) Corey-House synthesis of alkanes ?

(a) CH3I (b)

(c) (d)
(c) (d) 28. End product of the following sequence of reaction is

23. Choose the correct statement(s) about the following NBS Mg /ether CH CN
3
    
 
reaction. H3O

CH OH
3


I. The major product of the reaction is butyl-methyl
ether.
II. The major product of the reaction is 1-butene.
(a) (b)
III. The major product is formed by SN 2 reaction
mechanism.
IV. The major product is followed by E2 reaction
mechanism. (c) (d)
(a) I + III (b) II + IV
(c) I + IV (d) IV 29. Identify (Z) in the following reaction
24. Consider the following reaction Cl

+ Mg THF CO 2 H
(X) (Y) (Z)
1 mole

Br
X and Y are respectively Cl COOH
(a) both nitroethane
(b) both ethyl nitrite (EtONO
(a) (b)
(c) X = EtONO and Y = EtNO2
(d) X = EtNO2 and Y = EtONO
COOH COOH
25. Alkyl halides react with dialkyl copper reagents to give
COOH COOH
(a) Alkenes (b) Alkyl copper halides
(c) Alkanes (d) Alkenyl halides
(c) (d)
26. What would be the product formed when 1-Bromo-3-
chloro cyclobutane reacts with two equivalents of
metallic sodium in ether Br
ALKYL AND ARYL HALIDES 225

30. Replacement of Cl of chlorobenzene to give phenol 34. Which of the following is (are) true regarding
requires drastic conditions but chlorine of 2, 4- intermediate in the addition-elimination mechanism of
dinitrochlorobenzene is readily replaced because the reaction below ?
(a) NO2 make ring electron rich at ortho and para
(b) NO2 withdraws e– from meta position
(c) denotes e– at meta position NaOCH
3  intermediate 
 
(d) NO2 withdraws e– from ortho/para positions
31. Which chloroderivative of nitrobenzenes among the
following would undergo hydrolysis, most readily with
aqueous NaOH ? I. The intermediate is aromatic.
O2N NO2 NO2 II. The intermediate is resonance stabilized anion.
III. Electron withdrawing group on the benzene ring
(a) Cl (b) O2N Cl stabilize the intermediate
(a) I only (b) II only
O2N NO2 (c) I and III (d) II and III
O2N O2N 35. Which is the major product of the reaction of 2, 4–
dinitrochlorobenzene with methylamine ?
(c) O2N Cl (d) Cl

O2N O2N Cl
(a) (b)
32. Propyl benzene reacts with bromine in presence of light
or heat to give

(a)

(c) (d)

(b)
36. Arrange the following in increasing order of reactivity in
aromatic nucleophilic substitution reaction.
(c)

(d) (I) (II)

33. The reaction of 4-bromobenzyl chloride with NaCN in

ethanol leads to
(a) 4-bromo-2-cyanobenzyl chloride
(b) 4-cyanobenzyl cyanide (III) (IV)

(c) 4-cyanobenzyl chloride

(a) I < IV < III < II (b) IV < III < I < II
(d) 4-bromobenzyl cyanide
(c) I < IV < II < III (d) IV < I < II < III
ALKYL AND ARYL HALIDES 226
37. The use of the product obtained as a result of reaction
between acetone and chloroform is
(a) Hypnotic (b) Antiseptic (a) (b)

(c) Germicidal (d) Anaesthetic

38. Which plastic is obtained from CHCl 3 as follows
(c) (d)
HF 800 o C Polymerisa tion
CHCl 3 
 X   Y     
 Plastic
SbF 3 43. Which of the following sequence of reagent is best suited
(a) Bakelite (b) Teflon for the reaction shown below ?
(c) Polythene (d) Perspex
39. CCl4 is a well known fire extinguisher. However after using
it to extinguish fire, the room should be well ventilated.
This is because :
(a) (i) CH3MgBr, H3O+ (ii) H+/ (iii) HBr/H2O2
(a) it is inflammable at higher temperatures
(b) (i) CH3MgBr, H3O+ (ii) H+/ (iii) HBr
(b) it is toxic
(c) (i) CH3MgBr, H3O+ (ii) HBr
(c) it produces phosgene by reaction with water vapours
at higher temperatures (d) (i) HBr/ROOR (ii) CH3MgBr, H3O+
(d) it is corrosive 44. The major product of the following reaction is
40. When CHCl3 is boiled with NaOH, It gives
(a) Formic acid
Na / Ether 2 Br ,hv
Alc.KOH
(b) Trihydroxy methane     
(c) Acetylene
(d) Sodium formate (a) (b)
41. Which of the following is missing reagent in the following
reaction sequence ?

(c) (d)

45. What is the product of the reaction of the following

compound with alcoholic potassium hydroxide ?
(a) (CH3)3CO–K+ , Br2 Br
(b) (CH3)3CO–K+, HBr
(c) (CH3)3CO–K+, Br2/H2O CH3
(d) H2SO4, Br2
alc. KOH O3 (a) 1-methylcyclohexane only
C5H9Cl C5H8 C5H8O2 (b) 1-Methylcyclohexene only
42.
(CH3)2S
(c) 3-methylcyclohexene (major product),
A A
(no isomers) 1-methylcyclohexene (minor product)
Br2/CCl4
Br2/CCl4 (d) 3-methylcyclohexene only

Negative test Positive test

Which of the following is the structure of A ?
ALKYL AND ARYL HALIDES 227
Find out the structure of ‘A’ :
46. In the following reaction, the predominant substitution
and elimination products are
(a) (b)

(c) (d)

(a)
Objective Questions II
[One or more than one correct option]
49. Which of the following statements correctly
describes(s) E1 reactions of alkyl halides (RX) ?
(a) Rearrangements are sometimes seen
(b)
(b) Rate = k [base] [RX]
(c) Rate = k [RX]
(d) The reactions occur in two or more distinct steps
50. Which of the following can give E1 cb reaction?
(c)

(a) (b)

(d) (c) (d)

Cl CH3 H Cl
47. An organic compound C3H7Br(A) with alcoholic KOH 51.
forms C3H6 which decolorises Br2 in CCl4 but does not
H3 C H H3C H
gives a white precipitate with ammonical AgNO3. (A) on
reaction with KCN forms a product which on reduction (I) (II)
with Na/C2H5OH produces n-butyl amine. Hence, the Choose the correct statements about molecule I and II.
compound (A) is (a) I and II are diastereomers.
(a) n-propyl bromide (b) I and II are constitutional isomers.
(b) isopropyl bromide (c) Reactivity for SN1 path : II > I.
(c) 1, 1–dibromopropane (d) Reactivity to SN2 path : II > I.

(d) none of these 52. Which of the following phrases are correctly linked
with SN1 reaction ?
(a) Rate is affected by polarity of solvent
2 Br / hv Mg
48. A  B 
Et O  (b) Rearrangement is possible
2
(c) The strength of the nucleophile is important in
Conc.H SO
2 4 3 2 O / Zn  H O determining rate
D 
 E 
(d) The reactivity series is tertiary > secondary > primary
ALKYL AND ARYL HALIDES 228
53. Which of the following compounds will give SN1 reactant?
reaction? Ph
Ph
(a)
H3C H H3 C Cl
(a) (b)
(b) H Cl H H

CH2Ph CH2Ph
(c)
Ph Ph
H CH3 H CH3
(d) (c) (d)
Cl H H Cl
54. Which of the following compounds will not give SN2 CH2Ph CH2Ph
reaction?

(a) (b)
57.

(c) (d) Here the product can be ?

55. In the given reaction the products formed can be

(a) (b)

(a)

(c) (d)

(b)
58. Which of the following reactions involve free radical as
intermediate ?

(c) Cl  FeCl
2 3

(a)

(d)
(b) 2 Br / hv

(c) NBS

alc. KOH  E2 
56. Reactant  HCl
 Br /CCl
(d) 2 4


Which of the following molecule(s) is/are suitable

ALKYL AND ARYL HALIDES 229

59. Which of the following pair is correctly matched with The correct statement(s) is/are :
major products ? (a) substitution by a chlorine at ‘1’ will promote
Reaction Product substitution of fluorine by CN–.
(a) RX + AgCN RNC (b) substitution by a nitro group at ‘2’ will promote
(b) RX + KCN RCN substitution of fluorine by CN–.
(c) substitution by a cyano group at ‘1’ will promote
substitution of chloro by CN–.
(c) RX + KNO2
(d) substitution by a methoxy group at either ‘1’ or ‘2’
(d) RX + AgNO2 will discourage the reaction as a whole.
60. Which of the following alkanes cannot be synthesized 64. p–nitrofluorobenzene is more reactive than its meta isomer
by the Wurtz reaction in good yield ? in SNAr reaction with CH3ONa because
(a) nitro group from para position is in resonance with
(a) (b) lone pair of fluorine.
(b) nitro group from para position stabilizes the benzene
(c) (d) carbanion intermediate.
(c) nitro group from para position exert greater
61. Which of the following compounds give alcohol on
electronwithdrawing inductive effect than from meta
reaction with RMgX ?
position
(d) nitro group from para position gives less steric
(a) O2 (b) hindrance than from meta position to the attack of
nucleophile.
65. Consider the following statements and pick up the correct
(c) R – O – H (d) statements:
62. Consider the following SNAr treaction
(a) will react more
Heat
+ CH3 ONa  
readily than for SN1 reaction
The correct statement is (are)
(a) Cl will be substituted because it is a better leaving
group.
(b) F will be substituted because nitro from para position (b) will react more readily than for
facilitate this.
(c) after substitution of one halogen, substitution of the SN1 reaction
second halogen would become further more difficult.
(d) first chlorine and then fluorine would be substituted
subsequently.
63. Consider the following chlorofluorobenzene undergoing
(c) will react more readily than for
nucleophilic aromatic (SNAr) substitution reaction with
KCN
SN1 reaction
(d) SN1 reaction occurs in polar protic solvent

KCN

Heat 
ALKYL AND ARYL HALIDES 230

66. In which product formation takes place according to

Hofmann’s rule?

(a) Product C is
(a)

(b)
(b) Product D is

(c) (c) Product E is

(d)
(d) Product F is

67. Numerical Value Type Questions

69. How many substrates will show rearrangement during
SN1 reaction
Mark out the possible product.

(a)

(b)

(c)

(d)
70. If 1-chloro-4-methylcyclohexane is treated with KOH(aq.),
both substitution (SN2) and elimination (E2) reactions
occur simultaneously in comparable amount. In total, how
many substitution plus elimination products would
result?
71. 1, 3-dichlorocyclopentane exists in three stereo-isomeric
68.
forms, of which only two are chiral. If one mole of its
achiral stereoisomer is treated with exactly one mole of
NaOH in aqueous medium and, only mono substitution
(SN2) and mono-elimination (E2) occurs producing
chlorocyclopentanoland chlorocyclopentane, how many
different products are expected?
ALKYL AND ARYL HALIDES 231
72. If an etheral solution containing 2–chloropentane and
chloroethane is heated with sodium, how many different
alkanes would result through Wurtz’s reaction ? (1) 'X'RMgX
  3° Alcohol. Find
75. NH Cl 4
73. Find out numbers of possible E1 products from following
out value of ‘X’.
reaction.
76. Total number of RMgX are consumed in the following
reaction

74. How many of the following reactions, leads to the

formation of diastereomers.

HCl
(a)  
CCl4

HBr
Assertion Reason
(b)  
CCl4 (A) If both assertion and reason are correct and
reason is the correct explanation of
HBr
(c)   assertion.
CCl4
(B) If both assertion and reason are true but
reason is not the correct explanation of
assertion.
HCl
(d)   (C) If assertion is true but reason is false.
CCl4

(D) If assertion is false but reason is true.

77. Assertion (A) : Rate of reaction is dependent only on the
concentration of nucleophile in SN1 reactions.
Reason (R) : Polar solvent favours SN1 reaction.
HCl
(e)   (a) A (b) B
CCl4
(c) C (d) D
78. Assertion (A) : In SN1 mechanism, the product with
inversion of configuration is obtained in higher amount
compared to the product with the retention of
HCl configuration.
(f)  
CCl4
Reason (R) : Front side attack of nucleophile is hindered
due to the presence of leaving group in the vicinity.
(1) HBr + peroxide is used for AMk Add’ n (a) A (b) B
(2) HBr undergoes electrophilic addition (c) C (d) D
(3) NBS is used for allylic bramination. 79. Assertion (A) : Treatment of (+)-2-chlorobutane with
(4) Br2  FeBr3 is used to from electrrophile bromenium. aqueous NaCN gives laevo rotatory product.
Reason (R) : S N2 reaction leads to inversion of
configuration at the -carbon.
(a) A (b) B
(c) C (d) D
ALKYL AND ARYL HALIDES 232

80. Assertion (A) : Tertiary haloalkanes are more reactive nucleophile.

than primary haloalkanes towards elimination reactions. (a) A (b) B
Reason (R) : The + I-effect of the alkyl groups weakens (c) C (d) D
the C–X bond.
88. Assertion (A) : Ph–CO–CH2CH 2OCH3 has greater
(a) A (b) B reactivity for E1cB than for E2 reaction.
(c) C (d) D Reason (R) : A poor leaving group and acidic —H favour
81. Assertion (A): E1cb reaction is favoured by stabilisation E1cB mechanism.
of carbanion and poor leaving group. (a) A (b) B
Reason (R) : The reaction is kinetically of the second (c) C (d) D
order and unimolecular.
89. Assertion (A) : The carbon halogen bond in an aryl halide
(a) A (b) B is shorter than the carbon halogen bond in an alkyl halide.
(c) C (d) D 3
Reason (R) : A bond formed of an sp orbital should be
2
82. Assertion (A) : The presence of nitro group facilitates shorter than the corresponding bond involving an sp
nucleophilic substitution reaction in aryl halides. orbital.
Reason (R) : The intermediate carbanion is stabilized due (a) A (b) B
to the presence of the nitro-group. (c) C (d) D
(a) A (b) B 90. Assertion (A) : Alkyl iodide can be prepared by treating
(c) C (d) D alkyl chloride/bromide with NaI in acetone.
83. Assertion (A) : Benzyl bromide when kept in acetone - Reason (R) : NaCl/NaBr are soluble in acetone while NaI
water, produces benzyl alcohol. is not.
Reason (R) : The reaction follows SN2 mechanism. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D 91. Assertion (A) : Chlorination of allylic hydrogen is difficult
o o
84. Assertion (A) : 1 allylic halides are more reactive than 1 than vinylic hydrogen.
RX in SN1 reaction. Reason (R) : Allyl radical is stabilised by resonance.
Reason (R) : Allylic carbocation intermediate is stabilised (a) A (b) B
by resonance. (c) D (d) D
(a) A (b) B
Acetone
(c) C (d) D 92. Assertion (A) : CH3 – CH2 – Cl + NaI 

+ 2+
85. Assertion (A) : Heavy metal ions Ag or Pb decrease CH3 – CH2 – I + NaCl 
SN1 reactivity. Reason (R) : Acetone is polar Aprotic solvent and
Reason (R) : They aid ionisation of RX. solubility order of sodium halides decreases dramatically
(a) A (b) B in order NaI > NaBr > NaCl. The last being virtually
insoluble in this solvent and a 1° and 2° chloro alkane in
(c) C (d) D
o
acetone is completely driven to the side of Iodoalkane
86. Assertion (A) : Rate of ethanolysis of 1 halide by the precipitation reaction.
( O ) by SN1 mechanism is fast. (a) A (b) B
Br Me
(c) C (d) D
Reason (R) : Carbocation is stabilised by resonance.
93. Assertion (A) : Treatment of chloroethane with a
(a) A (b) B
saturated solution of AgCN gives ethyl isocyanide as
(c) C (d) D
the major product.
87. Assertion (A) : SN2 reaction of CH3––Br is faster in DMSO
Reason (R) : Cyanide (CN– ) is an ambident nucleophile.
than in H2O.
(a) A (b) B
Reason (R) : DMSO has greater capability to solvate
(c) C (d) D
ALKYL AND ARYL HALIDES 233
94. Assertion (A) : Wurtz’s coupling reaction of alkyl halide
is not suitable for an alkane containing an odd number of
carbons in the parent chain.
(B) (q) SN2
Reason (R) : Wurtz’s coupling reaction involves heating
of alkyl halides with sodium metal in ethereal solution.
(a) A (b) B
(c) C (d) D
95. Assertion (A) : p-nitrochlorobenzene is more reactive (C) (r) E1
than m-nitrochlorobenzene towards aromatic nucleophilic
substitution reaction.
Reason (R) : Nitro group from para and meta positions
has opposite effect in aromatic nucleophilic substitution
reaction. (D)
(a) A (b) B
(s) E2
(c) C (d) D
99. Column - I Column - II
96. Assertion (A) : A dichlorobenzene is slightly more
reactive than chlorobenzene towards an aromatic (A) CH3CH = CH2 (p) Side chain
nucleophilic substitution reaction. HBr , RCOOR substitution
 
Reason (R) : Chlorine has electron withdrawing effect on
aromatic ring. (B) CH3CH = CH2 
HBr
 (q) Anti-Markovnikov’ss
(a) A (b) B addition
(c) C (d) D
NBS , h
97. Assertion (A) : Chloral reacts with phenyl chloride to (C) C6 H5CH3   (r) Aromatic Substitution
form DDT.
Br2 / FeBr3
Reason (R) : It is an electrophilic substitution reaction (D) C6 H5CH3   (s) Markovnikov’s addition
(a) A (b) B 100. Match the column :
(c) C (d) D
Column - I Column - II
Match the following Wurtz reaction Number of dimerization
Each questions has two columns. Four product
options are given representing matching
Na
(A) CH3  Cl 
elements from Column-I and Column-II. Only dryether
 (p) 5
one of these four options corresponds to a
(B) CH 3  Cl  CH3  CH 2 (q) 6
correct matching. For each questions,
choose the correct option corresponding to Na
– Cl 
dryether

the correct matching.
98. Match the column I and II (C) CH3 – Cl + CH3 – CH2 (r) 3
Column - I Column - II – Cl + CH3 – CH2 – CH2
Reaction Type of Reaction
Na
– Cl 
dryether


(D) H2C = CH – CH = (s) 1

(A) (p) SN1 CH – CH2 – Cl + CH3
Na
– CH2 – Cl 
dryether

ALKYL AND ARYL HALIDES 234

104.
101. Column - I Column - II
(A) Sandmeyer reaction (p) C6H5COOAg, Br2/CCl4,
heat
(B) Balz-Schiemann (q) CH3CH2CH2Br, KI,
reaction acetone, heat
(C) Hunsdiecker reaction (r) C6H5N2Cl, HBF4, heat
(D) Finkelstein reaction (s) C6H5N2Cl, CuCl/HCl, heat
102. Match the column

105.

103. Column - I Column - II

(A) Anti-elimination (p) E1
(B) Must have acidic (q) Ei
-hydrogen
(C) No effect of solvent (r) E2
(D) carbocation (s) E1 CB
ALKYL AND ARYL HALIDES 235
Pragraph type questions 109. Transition state with least double-bond character will
Use the following passage, solve Q.106 to Q.112 be formed when methoxide reacts with
(a) 2-iodohexane to form 2-hexene
Passage
(b) 2-iodohexane to form 1-hexene
Aliphatic nucleophilic substitution is mainly of two type
S N 1 and S N2. S N2 reaction proceed with strong (c) 2-fluorohexane to form 2-hexene
nucleophile in polar aprotic solvent 3º halides do not (d) 2-fluorohexane to form 1-hexene
give SN2 reaction. Inverted products are obtained in 110. Isopropyl bromide on heating with a concentrated
this reaction and mechanism of reaction occurs through solution of alcoholic (ethanolic) KOH predominantly
the formation of transition state. gives
S N1 reaction proceed through the formation of (a) Propene (b) Propan-2-ol
carbocation in polar aprotic solvent. Solvent itself acts
(c) Propan-1-ol (d) Isopropyl ethyl ether
as nucleophile in this reaction. Racemization takes place
in SN1 reaction. 111. 2-Bromopropane is separately heated with aq.
CH3CO2Na or with CH3CH2ONa/CH3CH2OH, the major
106. Which of the following compounds will give SN1
product obtained in each case respectively are
reaction?
(a) Propene, isopropyl ethyl ether
(b) Isopropyl acetate, propene
(c) Isopropyl acetate, isopropyl ethyl ether
(a) (b)
(d) Propene in both the cases
112. 2-Bromopentane is heated with potassium ethoxide in
ethanol. The major product obtained is
(a) 2-Ethoxypentane (b) Pentene-1
(c) cis-Pentene-2 (d) trans-Pentene-2
(c) (d)
Use the following passage, solve Q.113 to Q.114
Passage
107. Which one of the following will give racemised product
The following E2 is carried out with different halogen
in C2H5OH?
substituent

(a) (b)

Four different reaction flasks, containing equimolar

concentration of sodium methoxide in methanol
(c) (d) solvent, were charged with equal moles of one of the
four halide in each flask and allowed to react under
108. Which one of the following will give SN2 reaction? identical experimental conditions as shown above.
After a week, the percentage yield of two alkenes in
each flask were measured and listed below
(a) (b) Flask No. Leaving Conj. % Yield % Yield
group Acid pKa of 2-hexene of 1-hexene
–
1. I –10 81 19
–
2. Br –9 72 28
–
3. Cl –7 67 33
(c) (d) –
4. F 3.2 30 70
ALKYL AND ARYL HALIDES 236
From the percentage yield of two products observed
(a) R – Cl > R – Br > R – I
with different leaving group, it was concluded that
both,ease of leaving group and steric hindrance to the (b) R – Br > R – Cl > R – I
–
approach of base CH3O to –H control the orientation (c) R – I > R – Br > R – Cl
of elimination reaction. (d) R – I = R – Br = R – Cl
113. Based on the above observation, which flask will have Use the following passage, solve Q.116 to Q.117
the largest amount of 1-hexene?
(a) 1 (b) 2
Passage
Type of elimination reaction in which least substituted
(c) 3 (d) 4
alkene is major product known as Hofmann’s elimiation.
Such reaction occur in following conditions :
(X) when base is bulky
114.
(Y) when leaving group is very poor such as fluoride,

ammonium group etc.

(a) (Z) when alkyl halide contain one or more double bonds.
116. What is the major product of the following reaction?

(b)

(c) (a)

(d) (b)

Use the following passage, solve Q.115

Passage (c)

Grignard reagent is usually prepared by

(d) None of these
Et O
2  RMgX
R  X  Mg  117. Which of the following will not produce Hofmann’s
Grignard reagent alkene as major product on reaction with strong base?
Et O
2  ArMgX
Ar  X  Mg 
Grignard reagent
(a) (b)
Grignard reagent acts as a strong base. Grignard reagent
carry out nucleophilic attact k in absence of acidic
hydrogen. Grignard reagent form complex with its ether
solvent. Complex formation with molecule of ether is an
important factor in the formation and stability of Grignard (c) (d)
reagent.
115. What is the correct order of reactivity of halides with Ans. (d)
magnesium ? Sol. -Cl is good leaving group.
ALKYL AND ARYL HALIDES 237

Use the following passage, solve Q.118 to Q.120

Passage
Cl 1Mole
2
Addition of X2 on alkene is electrophilic addition reaction. 119. 

CCl4
Reaction proceed through the formation of 3-membered
cyclic halonium ion. Nucleophile X– attacks from backside
of cyclic halonium ion hence total reaction is anti addition
reaction. If this reaction proceed in polar solvent then
solvent itself acts as nucleophile.

(a) (b)

Mechanism :

(c) (d)

2 3Cl ,CH OH
120.  Major product :
118. Which of the following statements is incorrect ?
(a) Symmertical trans alkene gives 2 products on reaction
with Br2/CCl4
(b) Symmetrical cis alkene gives 2 products on reaction (a) (b)
wit Br2/CCl4
(c) Trans alkenes give erythro product
(d) Cis alkenes gives threo product
(c) (d)
ALKYL AND ARYL HALIDES 238

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

1. Which of the following has the highest nucleophilicity ? (c) a mixture of diastereomers
(2000) (d) a single stereoisomer
(a) F– (b) OH– 7. Cyclobutylbromide on treatment with magnesium in dry ether
forms an organometallic compound (A). The organometallic
(c) CH3– (d) NH2– reacts with ethanal to give an alcohol (B) after mild
2. The order of reactivities of the following alkyl halides for a acidification. Prolonged treatment of alcohol (B) with an
SN2 reaction is (2000) equivalent amount of HBr gives 1-bromo-1-
methylcyclopentane (C). Write the structures of (A), (B) and
(a) RF > RCl > RBr > RI
explain how (C) is obtained from (B). (2001)
(b) RF > RBr > RCl > RI
8. Identify the set of reagents/reaction conditions X and Y in
(c) RCl > RBr > RF > RI the following set of transformations (2002)
(d) RI > RBr > RCl > RF
3. An SN2 reaction at an asymmetric carbon of a compound
always gives (2000)
(a) an enantiomer of the substrate
(a) X = dilute aqueous NaOH, 20°C, Y = HBr/acetic acid,
(b) a product with opposite optical rotation 20°C
(c) a mixture of diastereomers (b) X = concentrated alcoholic NaOH, 80°C, Y = HBr/acetic
(d) a single stereoisomer acid, 20°C
4. What would be the major product in each of the following (c) X = dilute aqueous NaOH, 20°C, Y = Br2/CHCl3, 0°C
reactions ? (2000)
(d) X = concentrated alcoholic NaOH, 80°C, Y = Br2/CHCl3,
0°C
(i) 9. How many structures of F is possible ? (2003)

(ii) (a) 2 (b) 5

(c) 6 (d) 3
10. (2003)
5. How would you synthesize 4-methoxyphenol from
bormobenzene in NOT more than five steps ? State clearly
the reagents used in each step and show the structures of
the intermediate compounds in your synthetic scheme.
(a) C6H5OC2H5 (b) C2H5OC2H5
(2001)
(c) C6H5OC6H5 (d) C6H5I
6. An SN2 reaction of an asymmetric carbon of a compound
always gives (2001) 11. Among the following, the molecule with the highest dipole
moment is (2003)
(a) an enantiomer of the substrate
(b) a product with opposite optical rotation (a) CH3Cl (b) CH2Cl2
(c) CHCl2 (d) CCl4
ALKYL AND ARYL HALIDES 239

12. (B) (c) (d)

(2004)

H3 O SOCl2

(C) 
CH3 NH 2
(D)
16. The correct statements for the following addition reactions
Identify A to D . is (are) MCQ(2017)
13. The following compound on hydrolysis in aqueous acetone
will give (2005)

(K)

(a) (M and O) and (N and P) are two pairs of enantiomers

(L) (b) Bromination proceeds through trans-addition in both
the reactions
(c) O and P are identical molecules
(M) (d) (M and O) and (N and P) two pairs of diastereomers
17. List-I contains reactions and List-II contains major products.
(2018)
(a) mixture of (K) and (L) (b) mixture of (K) and (M)
(c) only (M) (d) only (K)
14. When phenyl magnesium bromide reacts with t-butanol, the
product would be (2005)
(a) benzene (b) phenol
(c) t-butyl benzene (d) t-butyl phenyl ether
15. The major product of the following reaction is (2008)

(a) (b)
Match each reaction in List-I with one or more products in
List-II and choose the correct option.
(a) P - 1,5; Q - 2; R - 3; S - 4 (b) P - 1,4; Q - 2; R - 4; S - 3
(c) P - 1,4; Q - 1, 2; R - 3,4; S - 4 (d) P - 4,5; Q - 4; R - 4; S - 3,4
ALKYL AND ARYL HALIDES 240

18. The maximum number of possible isomers (including

20. The amount of energy required to break a bond is same as
stereoisomers) which may be formed on mono-bromination
the amount of energy released when the same bond is
of 1-methylcyclohex-1-ene using Br2 and UV light is
formed. In gaseous state, the energy required for homolytic
(2021) cleavage of a bond is called Bond Dissociation Energy (BDE)
19. The amount of energy required to break a bond is same as or Bond Strength. BDE is affected by s-character of the
the amount of energy released when the same bond is bond and the stability of the radicals formed. Shorter bonds
formed. In gaseous state, the energy required for homolytic are typically stronger bonds. BDEs for some bonds are
cleavage of a bond is called Bond Dissociation Energy given below
(BDE) or Bond Strength. BDE is affected by s-character of
the bond and the stability of the radicals formed. Shorter
bonds are typically stronger bonds. BDEs for some bonds
are given below

For the following reaction

light
CH 4  g   Cl2  g    CH3 Cl  g   HCl  g 
The correct statement is (2021)
Correct match of the C-H bonds (shown in bold) in Column
(a) Initiation step is exothermic with Hº  58kcal mol1
J with their BDE in Column K is (2021)
(b) Propagation step involving  CH 3 formation is

exothermic with Hº  2kcal mol 1

(c) Propagation step involving CH3 Cl formation is

endothermic with Hº  27kcal mol –1

(d) The reaction is exothermic with Hº  25kcal mol –1

(a) P - (iii), Q - (iv), R - (ii), S - (i)

(b) P - (i), Q - (ii), R - (iii), S - (iv)
(c) P - (iii), Q - (ii), R - (i), S - (iv)
(d) P - (ii), Q - (i), R - (iv), S - (iii)
ALKYL AND ARYL HALIDES 241

Note:

Find Answer Key and Detailed Solutions at the end of this book

ALKYL AND ARYL HALIDES

Please share your valuable feedback by

scanning the QR code.
ALCOHOLS, PHENOLS AND ETHERS
 Chapter 05 243

ALCOHOLS, PHENOLS AND ETHERS

1. INTRODUCTION Bond angle is slightly less due to LP-LP repulsion.

The compounds in which hydroxyl group (—OH) is attached to a

saturated carbon atom are called as Alcohols. The compounds in
which a hydroxyl group is attached to an unsaturated carbon
atom of a double bond are called as Enols. The saturated carbon
may be that of an alkyl, alkenyl, alkynyl, cycloalkyl or benzyl
group. However, if a hydroxyl group is attached to a benzene ring,
the compounds are called as Phenols.
The alcohols are further classified as : Monohydric (containing Lone pair of oxygen is delocalised on ring due to which C —
one —OH group), Dihydric (containing two —OH groups) and O bond length is less.
Trihydric (containing three —OH groups).
Alcohols find usage in industry as well as day to day life. For
example, ordinary spirit used for polishing wooden furniture is
chiefly ethanol. Sugar, cotton, paper are all made up of compounds
containing —OH groups. Phenols are used in several important
polymers such as Bakelite and in several drugs such as Aspirin.
Ethers are commonly used as solvents and anaesthetics.

2. CLASSIFICATION
Bond angle in methoxymethane is more than tetrahedral angle
due to repulsive interaction between the two bulky (R) groups.
The C—O bond length is same as in alcohols.

4. PHYSICAL PROPERTIES
4.1 Boiling Point
The boiling points of alcohols and phenols increase with increase
in the number of carbon atoms (increase in van der Waals forces).
In alcohols, the boiling point decreases with increase in branching
(decrease in Van der Waals forces due to decrease in surface
area).
The –OH group in alcohols and phenols contains a hydrogen,
bonded to an electronegative oxygen atom. Therefore, it is
3. STRUCTURES OF FUNCTIONAL GROUPS capable of forming intermolecular hydrogen bond, strength of
which is even greater than amine.
In alcohols, the oxygen of the —OH group is attached to carbon by
a sigma (  ) bond formed by the overlap of a sp3 hybridised
orbital of carbon with a sp3 hybridised orbital of oxygen. The
following figure depicts structural aspects of methanol, phenol
and methoxymethane.

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 244
It is due to the presence of strong intermolecular hydrogen 5.1 Alkane
bonding that alcohols and phenols have higher boiling points
Controlled Oxidation
corresponding to other classes of compounds, namely,
hydrocarbons, ethers and haloalkanes/haloarenes, amines of CH 4 +  O  
Cu tube
100 atm
CH 3OH
comparable molecular masses. 200°C

Their boiling points are lower than carboxylic acid which have 5.2 Alkene
even more strong H-bond. For isomeric alcohols boiling points
Markovnikov addition with carbocation rearrangements
decreases with increase in branching due to decrease in van der
Waals forces with decrease in size. The order of boiling point is
1° alcohol > 2° alcohol > 3° alcohol.
In ethers, boiling point is very less, and comparable to those of
alkane of comparable molecular mass due to less dipole moment
and absence of H-bonding.
4.2 Solubility 5.2.2 Oxymercuration-Demercuration
The solubility of alcohols and phenols in water is due to their Markovnikov addition without carbocation rearrangements
ability to form hydrogen bonds with water molecules. The
Mechanism :
solubility decreases with increase in the size of hydrophobic
group (R). Higher alcohol are insoluble. Branching increases
solubility, due to decrease in surface area of non-polar
hydrocarbon pan.
n-butylalcohol < isobutylalcohol < sec butylalcohol <
tert-butylalcohol

Lower ethers are water soluble but solubility is less than alcohol
due to less H-bonding with water and low polarity.
Refer to Table 1, 2, 3 and 4 for reference to physical properties of
alcohols, phenols and ethers.

5. PREPARATION OF ALCOHOLS
Example

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 245
5.2.3 Hydroboration-Oxidation 5.3.2 First order Substitution
Anti-Markovnikov addition Tertiary (and some Secondary) Halides

Mechanism : Example

Example

5.3.3 Grignard Reagent/Organolithium Reagent

Nucleophilic addition to the carbonyl group
5.2.4 SYN Hydroxylation

Reagents : Cold dil. KMnO4/NaOH or OsO4/H2O2

Example

(a) Addition to Formaldehyde- 1° Alcohol

Example

5.2.5 ANTI Hydroxylation

Reagents: Peroxy Acids followed by Acidic Hydrolysis
Example
(b) Addition to Aldehyde- 2° Alcohol

Example

5.3 Alkyl Halide

5.3.1 Second-order Substitution
Primary (and some Secondary) Halides
Example

 CH3 2 CHCH 2 CH 2  Br 

KOH
H O
2
  CH3  2 CHCH 2 CH 2  OH

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 246
(c) Addition to Ketone- 3° Alcohol Example

Example

2. Reduction of a ketone gives a secondary alcohol

Example

(d) Addition to anAcid Halide or Ester - 3°Alcohol

Example

3. Reduction of an acid or ester gives a primary alcohol

Example

NOTE
Bouveault-Blanc Reduction: A chemical reaction in which
Ester is reduced to primary alcohol using Absolute alcohol
(e) Addition to Ethylene Oxide - 1° Alcohol (with two carbon & sodium metal
atoms added)
O
Example ||
R  C  OR ' 
Na /C H OH
2 5
 R  COOH  R 'OH 1o Alcohol
Reactions of LiAlH4 and NaBH4

5.4 Carbonyl Compounds

5.4.1 Catalytic Hydrogenation

This method is usually not as selective or as effective as the

use of hydride reagents
5.4.2 Reduction with Metal Hydrides
1.Reduction of an aldehyde gives a primary alcohol

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 247
6.4 Tosylation
6. REACTIONS OF ALCOHOL
Tosylation is used to convert poor leaving group OH into good
leaving group OTs.
Example

6.1 Dehydration

EXA

6.5 Oxidiation
(a) Primary Alcohols

NOTE
Reactions with Al2O3, TbO2, P2O5 occur in gaseous phase.

6.2 Substitution

NOTE
Reaction of alcohol with SOCl2 in the pressure of pyridine
is known as Darzen’s process.
NOTE
1. Jones Reagent CrO3 + H2O/Acetone
6.3 Esterification
2. PCC - Pyridinium Chlorochromate
3. PDC - Pyridinium Dichromate
4. CrO3/Pyridine in CH2Cl2 - Collins Reagent
5. Cr(VI) oxidizes primary alcohol to aldehyde in anhydrous/
Esterification is catalyzed by an acid or base non-aqueous state and to carboxylic acid otherwise.

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 248
(b) Secondary Alcohols Common Phenols and Aromatic Ethers

Secondary alcohol in the presence of any oxidising agent is

oxidised to ketone.
(c) Tertiary Alcohols

MnO2 is an oxidising agent which oxidises only allylic, benzylic

& propargylic alcohols.

8. PREPARATION OF PHENOLS

7. PHENOL

8.1 Dow’s Process

This is industrial method for preparation of phenol. It oc-
curs through Benzyne Mechanism
Example

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 249
Example

8.2 Cumene process 9. REACTIONS OF PHENOLS

Example 9.1 Formations of Ethers

(a) Williamson Synthesis

(b) Nucleophillic Aromatic substitution

Example

8.3 Hydrolysis of Diazonium salts

8.4 Distillation of phenolic Acids with Sodalime

Example
9.2 Formations of Esters

Example

8.5 Benzene

Example

Example

8.6 Grinard Reagent

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 250
9.3 Fries Rearrangement Example

Example

Example

NOTE
Kinetic Control versus Thermodynamic control
1. Para isomer is the major product at 25ºC. It has lower H
and is formed more rapidly (rate controlled product)
2. Ortho isomer is the cheif product at 165ºC (equilibrium
controlled product). NOTE
Monobromination is achieved with non-polar solvents such
9.4 Reaction of Benzene Ring as CS2 to decrease the electrophilicity of Br2 and also to
minimize phenol ionization. In polar solvents such as water,
9.4.1 Hydrogenation phenol ionizes to phenoxide ion which is strongly activated
and therefore, bromination takes place at all the activated
Example positions
(b) Nitrosation
Example

9.4.2 Oxidation to Quinones

Example
Example

9.4.3 Electrophillic Substitution

(a) Halogenation

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 251
(c) Diazonium Salt Coupling - Azophenols

G is an electron releasing groups such as –OH, OR, –NR2,–NHR,

– NH2.
(d) Ring Alkylation
Example

Example

RX and AlCl3 give poor yields because AlCl3 co-ordinates with

lone pair of oxygen.
(e) Ring Acylation This reactions involves formation of carbene, :CCl2
This is achieved using Fries rearrangement. (h) Reaction of phenol with CCl4 in presence of base
(f) Kolbe’s Synthesis

(g) Reimer-Tiemann Synthesis of Phenolic Aldehydes

Mechanism :

CHCl3  OH   H 2 O : C Cl3

: C Cl3  Cl   : CCl2

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 252
(i) Formation of Aspirin Example

Example

10. ETHERS
10.1 Williamson Ethers Synthesis

Williamson ethers synthesis reaction can not occur with 3° alkyl

halide. In the presence of 3° alkyl halide we get an alkene.
1. Reduction of Phenol

2. Selctive reduction of Phenol

NOTE
Reduction of Phenol with HCHO
Substrate and Leaving group in williamson
synthesis
1. Leaving group X = Cl, Br, I, OTs etc.
2. Substrate - Alkyl group R’ must be primary.
10.2 Alkoxymercuration-Demercuration

This reactions follows Markovnikov orientation.

(j) Formation of Oil of Wintergreen

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 253
10.3 Bimolecular Dehydrations of Alcohols NOTE
This reactions is an industrial method for synthesis of ethers. Opening of Epoxide Ring
1. In acid catalyzed opening, nucleopile attacks on that
epoxide carbon from which more stable carbocation can be
made.
2. In base catalyzed opening, nucleophile attacks on the
11. REACTION OF ETHERS less hindered carbon.

11.1 Cleavage by HBr and HI

Example

11.2 Autoxidation
13. REACTION OF EXPOXIDES
13.1 Acid-catalyzed Opening

(a) In water

12. PREPARATION OF EPOXIDES

12.1 Peroxy Acid Epoxidation Anti stereochemistry is followed.

(b) In alcohols

The alkoxy group bonds to the more highly substituted carbon.

Example
12.1 Base-promoted cyclization of halohydrins

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 254
(c) Hydrohalic Acids (X= Cl, Br, I)
14. ACIDIC STENGTH
(i) Alcohols are weaker acids than thiols even though oxy-
gen is more electronegative than sulphur. Conjugate base
of alcohol i.e. RO– is more basic than RS– as in RO– nega-
tive charge is placed on smaller oxygen atom so it will
have more charge density. But in RS– negative charge is
13.2 Base-catalyzed Opening dispersed on bigger sulphur so it is a poor base and its
conjugate acid will be more acidic.Order of acidic strength
(a) with Alkoxides
of some of some of the chemical are given as:
RSO3 H > RCOOH > Phenol > H 2 O > ROH
HC = CH > NH 3 > CH 2 = CH 2 > CH 3
(ii) All alcohols
alcohols (except
(except CH
CH33OH)
OH) are weaker acids than H2O
due to +I effect of alkyl group. CH3OH is slightly stronger
than H2O. Phenols are stronger than alcohol due to elec-
The alkoxy group bonds to the less highly substituted carbon tron withdrawing benzene ring & resonance stabilized phe-
noxide ion. Alkoxide ions, the conjugate base of alcohol
Example
have no resonance so they are less stable and more basic.
Phenol is weaker than carboxylic acid which have strong
electron withdrawing carbonyl group and more stable reso-
nating structures.

15. TESTS FOR ALCOHOLS, PHENOLS & ETHERS

15.1 Analysis of alcohols-Characterization
(a) Alcohols dissolve in cold concentrated sulfuric acid. This
(b) With organometallics property they share with alkenes, amines, practically all
compounds containing oxygen, and easily sulfonated com-
pounds. (Alcohols, like other oxygen-containing com-
pounds, form oxonium salts which dissolve in the highly
polar sulfuric acid.)
(b) Alcohols are not oxidized by cold dilute, neutral permanga-
nate (although primary and secondary alcohols are oxidized
by permanganate under more vigorous conditons.) How-
ever, as we have seen, alcohols often contain impurities
Example that are oxidized under these conditions, and so the per-
manganate test must be interpreted with caution.
(c) Alcohols do not decolorize bromine in carbon tetrachlo-
ride. This property serves to distinguish them from alkenes
and alkynes.
Alcohols are further distinguished from alkenes and alkynes
and from nearly every other kind of compound by their
oxidation by chromic anhydride (CrO3) in aqueous sulfuric
acids. Within two seconds, the clear orange solution tums
blue-green and becomes opaque.
ROH + HCrO 4  Opaque, blue green
1° or 2° Clear

Tertiary alcohols do not give this test. Aldehydes do, but

are easily differentiated in other ways.
(d) Reactions of alcohols with sodium metal with the evolution
of hydrogen gas is of some use in characterization. A wet
compound of any kind, of course, will do the same thing,
until the water is used up.

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 255
(e) The presence of the -OH group in a molecule is often indi- The reaction involves oxidation, halogenation and cleavage
cated by the formation of an ester upon treatment with an
acid chloride or anhydride. Some esters are sweet-smelling;
others are solids and sharp melting points, and can be de-
rivatives in identifications. If the molecular formulas of start-
ing material and product are determined, it is possible to
calculate how many -OH groups are present.
(f) Whether an alcohol is primary, secondary or tertiary is shown
by the Lucas test, which is based upon the difference in
reactivity of the three classes towards hydrogen halides.
Alcohols (of not more than six carbons) are soluble in the
Lucas reagent, a mixture of concentrated hydrochloric acid
and zinc chloride. The corresponding alkyl chlorides are
insoluble. Formation of a chloride from an alcohol is indi-
cated by the cloudiness that appears when the chloride As would be expected from the equations, a compound of
separates from the solution. Hence, the time required for
structure also gives a positive test.
cloudiness to appear is a measure of the reactivity of the
alcohol.
A tertiary alcohol reacts immediately with the Lucas reagent,
and a secondary alcohol reacts within five minutes. A pri-
mary alcohol does not react appreciably at room tempera- In certain special cases this reaction is used not as a test,
ture. Benzyl alcohol and allyl alcohol react as rapidly as but to synthesize the carboxylic acid, RCOOH. Here,
teritary alcohols with the Lucas reagent. Allyl chloride, how- hypobromite or the cheaper hypochlorite would probably
ever, is soluble in the reagent. be used.
(g) Whether or not an alcohol contains one particular struc-
15.2 Analysis of Glycols, Periodic Acid Oxidation
tural unit is shown by the iodoform test. The alcohol is
treated with iodine and sodium hydroxide (sodium Upon treatment with periodic acid, HIO4, compounds
hypoiodite, NaOI). An alcohol of the structure yields a yel- containing two or more –OH or C=O groups attached to
low precipitate of iodoform (CHI3m.p. 119°C). adjacent carbon atoms undergo oxidation with cleavage of
carbon-carbon bonds.

15.3 Miscellaneous Tests

(a) Ceric Ammonium Nitrate Test - Alcohols give red colour
with this reagent.
Ce(NH4)2(NO3)6 +RCH2OH  Ce(NH4)2(NO3)5 + RCOOH +
HNO3
(b) Potassium Dichromate Test - Alcohol turn orange dichro
mate to green. Tertiary Alcohol do not give this first.

(c) Ester Test - Alcohol gives fruity smell of Ester with

carboxylic acid.

(d) Methanol Forms oil of winter green with salicylic acid.

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 256
15.4 Victor Meyer’s Test 15.5.2 Alcohol and Ethers
(a) Alcohols react with Na to give H2 but not ethers
(b) Alcohols give fumes of HCl with PCl5 but not ethers
15.5.2 Sodium Bicarbonate Test
Phenol, ROH and H2O do not displace CO2 from carbonate &
bicarbonates but RCOOH & RSO3H gives brisk effervescence of
CO2 which proves that RCOOH & RSO3H are stronger acids H2CO3
but phenol is weaker acid than HCOOH. Nitrophenols also give
effervescence of CO2 with Na2CO3. Trinitrophenol (Picric Acid) is
highly acidic due to strong electron withdrawing effect of
threegroups its acidic strength is comparable to that of carboxy-
lic acids.Its anion is highly resonance stabilised.
 
RCOOH  NaHCO3  RCO O N a  CO 2   H 2 O
Ph  OH  NaHCO3  No Reaction

15.5 Differentiations Tests

15.5.1 Alcohol and phenols
1. Litmus Test : Phenol turns blue litmus red but not alcohols

2. FeCl 3 : Phenol  Neutral

 FeCl 3
 Blue–Violet

3. Coupling reactions:

Phenol+Diazonium Salt  

Weakly basic
medium
 Yellow or
15.5.4 FeCl3 Test
Orange Dye
Phenol gives characteristic purple colour with FeCl3 but alcohols
do not react with FeCl3 Carboxylic acids also form buff coloured
Diazonium Salt + Alcohol  
Weakly basic
medium
 No precipitate with FeCl3. Only acetic acid forms red coloured pre-
Reaction cipitate with FeCl3, so it can be used as a test for acetate salts.

4. Bromine Water Test:

Diazonium Salt + Alcohol +Br2 

H 2O
 No Reaction

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 257
Table 1 : Physical Properties of Selected Alcohols

IUPAC Name Common Name Formula MP(ºC) BP(ºC) Density

methanol methyl alcohol CH 3OH –97 65 0.79
ethanol ethyl alcohol CH 3CH 2OH –114 78 0.79
1-propanol n-propyl alcohol CH 3CH 2CH 2OH –126 97 0.80
2-propanol isopropyl alcohol (CH 3)2CHOH –89 82 0.79
1-butanol n-butyl alcohol CH 3(CH2) 3OH –90 118 0.81
2-butanol sec-butyl alcohol CH3CH(OH)CH2CH3 –114 100 0.81
2-methyl-1-propanol isobutyl alcohol (CH3)2CHCH2OH –108 108 0.80
2-methyl-2-propanol t-butyl alcohol (CH3)3 COH 25 83 0.79
1-pentanol n-pentyl alcohol CH3(CH2) 4OH –79 138 0.82
3-methyl-1-butanol isopentyl alcohol (CH 3) 2CHCH2CH2OH –117 132 0.81
2,2- dimethyl neopentyl alchol (CH 3) 3CCH2OH 52 113 0.81
–1–propanol
cyclopentanol cyclopentyl alcohol cyclo-C5H9OH –19 141 0.95
1-hexanol n-hexanol CH3(CH2)5OH 52 156 0.82
cyclohexanol cyclohexyl alcohol cyclo-C6H5OH 25 162 0.96
1-heptanol n-heptyl alcohol CH3(CH 2)6OH –34 176 0.82
1-octanol n-octyl alcohol CH3(CH2) 7OH –16 194 0.83
1-nonanol n-nonyl alcohol CH3(CH2) 8OH –6 214 0.83
I-decanol n-decyl alcohol CH3(CH 2)9OH 6 233 0.83
2-propen-1-ol allyl alcohol H2 C=CH–CH2OH –129 97 0.86
phenylmethanol benzyl alcohol Ph—CH2OH –15 205 1.05
diphenylmethanol diphenylcarbinol Ph 2CHOH 69 298
triphenylmethanol triphenylcarbinol Ph 3COH 162 380 1.20
1, 2-ethanediol ethylene glycol HOCH 2CH 2OH –13 198 1.12
1, 2-propanediol propylene glycol CH3CH(OH)CH2OH –59 188 1.04
1, 2, 3-propanetriol glycerol HOCH 2CH(OH)CH2OH 18 290 126

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 258

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 259

Table 3: Comparison of the Boiling Points of Ethers, Alkanes and Alcohols of Similar
Molecular Weights

Table 4: Solubility ofAlcohols in Water (at 25°C)

Alcohol Solubility in Water
methyl miscible
ethyl miscible
n-propyl miscible
t-buty1 miscible
isobutyl 10.0%
n-butyl 9.1%
n-pentyl 2.7%
cyclohexyl 3.6%
n-hexyl 0.6%
phenol 9.3%
hexane-1, 6-diol miscible

Table 5: Acid-Dissociation Constants of Representative Alcohols

Alcohol Structure Ka pKa

methanol CH3–OH 3.2 × l0–16 15.5
ethanol CH3CH2– OH 1.3 × 10–16 15.9
2-chloroethanol Cl–CH2–CH2–OH 5.0 × 10–15 14.3
2-2-trichloroethanolCl3C–CH2–OH 6.3 × 10–13 12.2
isopropyl alcohol (CH3)2CH–OH 3.2 × 10–17 16.5
t-butyl alcohol (CH3)3C–OH 1.0 × 10–18 18.0
cyclohexanol C6H11 –OH 1.0 × 10–18 18.0
phenol C6H5 – OH 1.0 × l0 –10 10.0
Comparison with other Acids
water H2O 1.8 × 10–16 15.7
acetic acid CH3COOH 1.6 × 10–5 4.8
hydrochloric acid HCl 1.6 × 10+2 –2.2

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 260

SUMMARY

SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 261

SOLVED EXAMPLES

Objective Questions I [Only one correct option]

Example – 1 Sol. The reason for the lesser volatility of alcohols than ethers
Hydrogen bonding is maximum in is the intermolecular associations of a large number of
(a) ethanol (b) diethyl ether molecules due to hydrogen bonding as -OH group is highly
(c) ethyl chloride (d) triethyl amine polarized.
Ans. (a)
Sol. Ethanol is capable in forming intermolecular H-bonds:

No such hydrogen bonding is present in ethers.

Example – 2
Example – 4
Acid catalyzed hydration of alkenes except ethene leads to
the formation of In the hydroboration-oxidation reaction of propene with
diborane, H2O2 and NaOH, the organic compound formed
(a) mixture of secondary and tertiary alcohols is:
(b) mixture of primary and secondary alcohols (a) CH3CH2OH (b) CH3CHOHCH3
(c) secondary or tertiary alcohol (c) CH3CH2CH2OH (d) (CH3)3COH
(d) primary alcohol Ans. (c)
Ans. (c)
Sol. Water adds to more reactive alkenes in the presence of acids Sol. CH 3  CH  CH 2 
Hydroboration
oxidation
 CH 3  CH 2  CH 2
|
to yield alcohols. OH
Example – 5
CH 3
|
Phenyl magnesium bromide reacts with methanol to give
H2O H
 H 3 C  C OH 3 alcohol
H 3 C  C  CH 2 
| |
  (a) a mixture of anisol and Mg(OH)Br
CH3 CH 3 (b) a mixture of benzene and Mg(OMe)Br
(c) a mixture of toluene and Mg(OH)Br
 

H2O H
CH 3  CH  CH 2    CH 3  C H  CH 3 2  alcohol (d) a mixture of phenol and Mg(Me)Br
|
OH
Ans. (b)
Example – 3 Sol.
An ether is more volatile than an alcohol having the same
molecular formula. This is due to
(a) dipolar character of ethers
(b) alcohols having resonance structures
(c) intermolecular hydrogen bonding in ethers
(d) intermolecular hydrogen bonding in alcohols
Ans. (d)
ALCOHOLS, PHENOLS AND ETHERS 262

Example – 6 Example – 8
In the following sequence of reactions, During dehydration of alcohols to alkenes by heating with
concentrated H2SO4 the initiation step is
(a) protonation of alcohol molecule
the compound ‘D’ is (b) formation of carbocation
(a) butanal (c) elimination of water
(b) n-butyl alcohol (d) formation of an ester
(c) n-propyl alcohol Ans. (a)
(d) propanal Sol. Dehydration of alcohol to alkene in presence of
Ans. (c)
concentrated H 2SO4 involves following steps:
Sol.

Example – 9
Example – 7
Among the following compounds which can be dehydrated
Consider the following reaction
very easily ?
C2H5OH + H2SO4  Product
Among the following, which one cannot be formed as a
product under any conditions ? (a) CH3CH2CH2CH2CH2OH (b)
(a) Ethyl hydrogen sulphate
(b) Ethylene
(c) Acetylene (c) (d)
(d) Diethyl ether
Ans. (c)
Ans. (c)
Sol.
Sol. The ease of dehydration of alcohols is tertiary  secondary
 primary according to the order of stability of the
carbocations.
CH3 CH3
| |
H
CH3  CH2  C  CH2  CH3  CH3  CH2  C  CH2  CH3
| 
OH

The more stable carbocation is generated thus more easily

it will be dehydrated.

(a),(b),(d) may be formed but c is never formed

ALCOHOLS, PHENOLS AND ETHERS 263
(b) CrO 3
Example – 10 (c) PCC (Pyridinium Chlorochromate)
The main product of the following reaction is
Conc. H2SO4
(d) KMnO 4
C6H5CH2CH(OH)CH(CH3)2  ?
Ans. (c)
PCC
Sol. R  CH 2  OH   R  CHO
(a)
It is mild oxidising agent.
Example – 14
In CH3CH2OH, the bond that undergoes heterolytic cleavage
(b) most readily is
(a) C—C (b) C—O
(c) C—H (d) O—H
Ans. (d)
(c)
Sol. Reaction of alcohol with Na indicates that (O-H) bond is
most readily broken
2ROH  2Na  2RONa  H 2
(d)
Example – 15
Ans. (a) Among the following compounds, the strongest acid is
Sol. Double bond conjugated with benzene ring is most stable.
Trans porduct is more stable than cis. (a) (b) C6H6
(c) C2H6 (d) CH3OH
Example – 11 Ans. (d)
The best reagent to convert pent-3-en-2-ol into pent-3-en- Sol. Alcohols behave as acid due to the polar bond of O-H
2-one is
(a) MnO2 Example – 16
(b) Pyridinium chlorochromate
From amongst the following alcohols the one that would
(c) acidic dichromate react fastest with conc HCl and anhydrous ZnCl2, is
(d) acidic permanganate (a) 2-butanol (b) 2-methylpropan-2-ol
Ans. (b) (c) 2-methylpropanol (d) 1-butanol
Sol. Pyridinium chlorochromate oxidises an alcoholic group Ans. (b)
selectively in the presence of carbon-carbon double bond.
Sol. The reagent,conc. HCl and anhydrous ZnCl2 is Lucas
Example – 12
A liquid was mixed with ethanol and a drop of concentrated reagent, which is used to distinguish between 10 , 20 and 30
H2SO4 was added. A compound with a fruity smell was alcohols.
formed. The liquid was
30 alcohol + Lucas reagent  Immediate turbidity.
(a) CH3OH (b) HCHO
(c) CH3COCH3 (d) CH3COOH 20 alcohol  Lucas reagent  Turbidity after 5 mins.
Ans. (d)
10 alcohol  Lucas reagent  No reaction.
Sol. Fruity smell is due to ester formation which is formed
between ethanol and acid. Thus, the required alcohol is 2-methyl propan -2-ol, i.e.,
Example – 13
The most suitable reagent for the conversion of
R  CH 2  OH  R  CHO is :

(a) K 2 Cr2 O 7
ALCOHOLS, PHENOLS AND ETHERS 264
Example – 17 Sol.
In the Victor-Meyer’s test, the colour given by 1o, 2o and OH OH
3o alcohols are respectively: NO2
NO2
(a) Red, blue, violet H2 SO4
 
(b) Colourless, red, blue HNO3

(c) Red, colourless, blue

(d) Red, blue, colourless
NO 2
Ans. (d)
Example -20
Phthalic acid reacts with resorcinol in the presence of
concentrated H2SO4 to give;
Sol.
(a) Phenolphthalein (b) Fluorescein
(c) Alizarin (d) Coumarin
Example – 18 Ans. (b)
Which one of the following statements is not correct? Sol.
(a) Alcohols are weaker acids than water
(b) Carbon- oxygen bond length in methanol, CH3OH is
shorter than that of C–O bond length in phenol.
(c) Acid strength of alcohols decreases in the following
order RCH2OH > R2CHOH> R3COH

(d) The bond angle in methanol is 108.90

Ans. (b)
Example – 21
Sol. CH 3 - OH The structure of the compound that gives a tribromo
derivative on treatment with bromine water is

(a) (b)

In phenol C - O bond acquire some double bond character

due to resonance so B.L of CH 3 OH > C6 H 5 OH (c) (d)
Example – 19
Phenol, when first reacts with concentrated sulphuric acid
and then concentrated nitric acid, gives Ans. (a)
(a) o–nitrophenol (b) p–nitrophenol Sol.
(c) Nitrobenzene (d) 2, 4,6–trinitrophenol
Ans. (d)
ALCOHOLS, PHENOLS AND ETHERS 265

Example – 22
Example – 24
Phenol is heated with a solution of mixture of KBr and
KBrO3. The major product obtained in the above reaction is Sodium phenoxide when heated with CO2 under pressure at
125ºC yields a product which on acetylation produces C.
(a) 2-bromophenol (b) 3-bromophenol
(c) 4-bromophenol (d) 2, 4, 6-tribromophenol
Ans. (d)
125º H 
CO2 
5 Atm  B 
Ac O  C
Sol. KBr( aq ) +KBrO3( aq )  Br2( aq ) 2

This bromine reacts with phenol gives 2, 4, 6 

tribromophenol
The major product C would be :

(a) (b)

Example – 23
Phenol, when it first reacts with concentrated sulphuric acid (c) (d)
and then with concentrated nitric acid, gives
(a) 2, 4, 6-trinitrobenzene (b) 2,4,6-tri-nitrophenol
(c) p-nitrophenol (d) nitrobenzene Ans. (d)
Sol.
Ans. (b)
Sol.

Example – 25
In the following compounds

The order of acidity is

(a) III > IV > I > II (b) I > IV > III > II
(c) II > I > III > IV (d) IV > III > I > II
ALCOHOLS, PHENOLS AND ETHERS 266
Ans. (d) Ans. (c)
Sol. order is based on -I and -R effect (which stabilize the
phenoxide ion)
Example – 26
Which of the following reagents may be used to distinguish Sol.
between phenol and benzoic acid ?
(a) Aqueous NaOH (b) Tollen’s reagent
(c) Molisch reagent (d) Neutral FeCl3 Example – 31
Ans. (d) Benzene diazonium chloride on reaction with phenol in
weakly basic medium gives
Sol. FeCl3 forms violet complex with phenol whereas it forms
(a) p-Hydroxy azobenzene
buff coloured precipitate with Benzoic Acid
(b) o-Hydroxy azobenzene
(c) diphenyl ether (d) diphenyl amine
Example – 27 Ans. (a)
Allyl phenyl ether can be prepared by heating: Sol.
(a) C6H5Br + CH2 = CH – CH2 – ONa
(b) CH2 = CH – CH2 – Br + C6H5ONa
(c) C6H5 – CH = CH – Br + CH3 – ONa
(d) CH2 = CH – Br + C6H5 – CH2 – ONa
Ans. (b)
Sol. CH 2  CH  CH 2  Br  C6 H 5ONa 

CH 2  CH  CH 2  O  C 6 H 5 Fill in the Blanks

Example – 28
Example – 32
Williamson synthesis of ether is an example of : A ................. diol has two hydroxyl groups on .................
(a) Electrophilic addition carbon atoms.
(b) Nucleophilic addition Ans. (Vicinal; adjacent)
(c) Electrophilic substitution Sol. Vicinal; adjacent
(d)Nucelophilic substituion
Ans. (d) Example – 33
Sol. Williamson synthesis is nucleophilic substitution reaction. Ethanol vapour is passed over heated copper and the product
is treated with aqueous NaOH. the final product is
.....................
Example – 29
Ans. (aldol)
Diethyl ether on heating with conc. HI gives two moles of Sol.
(a) ethanol (b) iodoform
(c) ethyl iodide (d) methyl iodide
Ans. (c)
Sol. CH 3 -CH 2 -O-CH 2 -CH 3 +HI  2C 2 H 5 l
Example – 30
Which of following product obtain in Reimer-Tiemann
reaction?
(a) Phenol (b) benzaldehyde
(c) Salicylaldehyde (d) Salicylic acid
ALCOHOLS, PHENOLS AND ETHERS 267

Example – 34 Example – 37
Aliphatic ethers are purified by shaking with a solution of Match the column
ferrous salt to remove ............... which are formed on
Match the following choosing one item from column ‘X’
prolonged standing in contact with water.
and the appropriate item from column Y.
Ans. (Peroxides)
X Y
Sol. Peroxides: H 2 O2 +Fe 2+  H2 O+Fe3+ (A) Williamson’s synthesis (P) tert-alcohol
Assertion Reason (B) Neutral FeCl3 test (Q) Ether
(A) If both assertion and reason are correct (C) Lucas test (R) Phenol
and reason is the correct explanation of Ans. (A-q, B-r, C-p)
assertion. Sol. (a). Williamson's synthesis is used for the preparation of
(B) If both assertion and reason are true but ether.
reason is not the correct explanation of (b). Phenol gives distinct colour with neutral FeCl3 solution.
assertion. (c). Lucas test is used for distinction between 1°, 2° and 3°
alcohols.
(C) If assertion is true but reason is false.
(D) If assertion is false but reason is true.
Example – 38
Example – 35
Write the structures of the products :
Assertion (A): Solubility of n-alcohol in water decreases HI (excess)
with increase in molecular weight. (CH3)2 CH—OCH3 
heat
Reason (R): The reactive proportion of the hydrocarbon
part in alcohols increases with increasing Sol.  CH3 3 CH-O-CH3 
HI
 CH3 -CH -CH3 +CH 3 I
molecular weight which permits enhanced |
hydrogen bonding with water. OH
(a) A (b) B Example – 39
(c) C (d) D
Ans. (c) 2, 2-dimethyloxirane can be cleaved by acid (H+). Write
mechanism.
R-OH  Hydrophilic
Sol.

Hydrophobic
Increasing molecular weight increases hydrocarbon (R)
proportion that lowers the solubility in water. Sol.

Example – 36
True/False
Assertion (A): p-nitrophenol is a stronger acid than
o-nitrophenol. Example – 40
Reason (R): Intramolecular hydrogen bonding make the The yield of a ketone when a secondary alcohol is oxidised
o-isomer weaker acid than the p-isomer. is more than the yield of aldehyde when a primary alcohol is
oxidised.
(a) A (b) B
Ans. (T)
(c) C (d) D
Sol. Aldehydes (from primary alchols) may further be
Ans. (a)
oxidized easily to acids as compared to ketones (from
Sol. O-nitrophenol contains intramolecular hydrogen bonding
between hydrogen of hydroxyl group and oxygen of nitro secondary alchols).
group. Due to this the hydrogen atom of hydroxyl group is
firmly attached to molecule and cannot be easily lost. Such
intramolecular hydrogen bonding is not present in p-
nitrophenol. Thus, p-Nitrophenol is stronger acid than o-
nitrophenol. This is also supported by pKa values. The
pKa of p-nitrophenol is 7.1 which is lower than that of o-
nitrophenol (pKa=7.2). Stronger acid has lower pKa value.
ALCOHOLS, PHENOLS AND ETHERS 268

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Introduction and Preparation of Alcohols 6. Which of the following reagents convert the propene to
1-propanol
1. Glycerine has
(a) H2O, H2SO4 (b) Aqueous KOH
(a) One primary and two secondary –OH groups
(c) MgSO4, NaBH4/H2O (d) B2H6, H2O2, OH–
(b) One secondary and two primary –OH groups
7. Ethylene reacts with Baeyer’s reagent to give
(c) Three primary –OH groups
(a) Ethane (b) Ethyl alcohol
(d) Three secondary –OH groups
(c) Ethylene glycol (d) None of these
2. The structural formula of cyclohexanol is
8. The product of the following reaction is

(a) (b)

(a) 2-pentanol (b) pentane

(c) pentan-2-one (d) 1-pentanol
(c) (d) 9. Oxymercuration-demercuration reaction of 1-methylcyclohexene
gives
3. The compound which gives the most stable carbonium ion (a) trans-2-methyl cyclohexanol
on dehydration is
(b) cis-2-methylcyclohexanol
(a)
(c) 1-methylcyclohexanol
(d) mixture of cis- and trans-2-methylcyclohexanol
10. 2-phenylethanol may be prepared by the reaction of
phenylmagnesium bromide with
(b)
(a) HCHO (b) CH3COCH3

(c)
(c) (d) CH3CHO

11. Methanol is industrially prepared by

(d)
(a) Oxidation of CH4 by steam at 900°C
4. Propan-1-ol can be prepared from propene by
(b) Reduction of HCHO using LiAlH4
(a) H2O/H2SO4
(c) Reaction HCHO with a solution of NaOH
(b) Hg(OAc)2/H2O followed by NaBH4
(d) Reduction of CO using H2 and ZnO–Cr2O3
(c) B2H6 followed by H2O2
(d) CH3CO2H/H2SO4
Chemical Properties of Alcohols
5. Chlorination of toluene in the presence of light and heat 12. Alcohols react with Grignard reagent to form
followed by treatment with aqueous NaOH gives (a) Alkanes (b) Alkenes
(a) o-cresol (b) p-cresol (c) Alkynes (d) All of these
(c) 2, 4-dihydroxy toluene (d) Benzoic acid
ALCOHOLS, PHENOLS AND ETHERS 269
13. Ethylene may be obtained by dehydration of which of the 20. During dehydration of alcohols to alkenes by heating with
following with concentrated H2SO4 at 160–170°C conc. H2SO4 the initiation step is
(a) C2H5OH (b) CH3OH (a) Protonation of alcohol molecule
(c) CH3CH2CH2OH (d) (CH3)2CHCH2OH (b) Formation of carbocation
14. Ethyl alcohol is heated with conc. H2SO4. The product formed is (c) Elimination of water
(d) Formation of an ester

(a) (b) C2H6 21. Which will dehydrate most easily

(a) 3-methyl-2-butanol (b) Ethyl alcohol
(c) C2H4 (d) C2H2
(c) 2-methyl propane-2-ol (d) 2-methyl butan-2-ol
15. Conc. H2SO4 reacts with C2H5OH at 170°C to form
22. In the following series of chemical reactions, identify Z
(a) CH3COCH3 (b) CH3COOH
(c) CH3CHO (d) C2H4
16. HBr reacts fastest with
(a) (b)
(a) 2-Methylpropan-1-ol (b) 2-Methylpropan-2-ol
(c) Propan-2-ol (d) Propan-1-ol
(c) (d)
17. Isopropyl alcohol heated at 300°C with copper catalyst to
form
(a) Acetone (b) Dimethyl ether 23. What is Z in the following sequence of reactions ?
(c) Acetaldehyde (d) Ethane PCl 
Z 5  X Alc
. KOH i Conc. H 2SO 4
 Y     Z
18. Which of the following vapours passed over heated copper ii  H 2O ; boil
to form acetone (a) CH3CH2CH2OH (b) CH3CHOHCH3

(a) (c) (CH3CH2)2CHOH (d) CH3CH = CH2

24. An organic compound A reacts with sodium metal and forms
(b) B. On heating with conc. H2SO4, A gives diethyl ether. A and
B are respectively
(a) C2H5OH and C2H5ONa
(b) C3H7OH and C3H7ONa
(c)
(c) CH3OH and CH3ONa

(d) (d) C4H9OH and C4H9ONa

25. Which of the following will not react with NaOH
19. Which of the following is not characteristic of alcohols
(a) They are lighter than water
(b) Their boiling points rise fairly uniformly with increasing
molecular weight
(a) (b) C2H5OH
(c) Lower members are insoluble in water and organic
solvents but solubility regularly increases with
molecular weight
(d) Lower members have pleasant smell and burning taste,
while higher members are odourless and tasteless (c) CH3CONH2 (d) CH(CN)3
ALCOHOLS, PHENOLS AND ETHERS 270
26. Compound ‘A’ reacts with PCl5 to give ‘B’ which on treatment 34. The increasing order of acidity among phenol, p-methylphenol,
with KCN followed by hydrolysis gave propanoic acid as m-nitrophenol and p-nitrophenol is
the product. What is ‘A’
(a) m-nitrophenol, p-nitrophenol, phenol, p-methylphenol
(a) Ethane (b) Propane
(b) p-methylphenol, m-nitrophenol, phenol, p-nitrophenol
(c) Ethyl chloride (d) Ethyl alcohol
(c) p-methylphenol, phenol, m-nitrophenol, p-nitrophenol
27. For the reaction, (d) Phenol, p-methylphenol, p-nitrophenol, m-nitrophenol
C 2 H 5OH  HX ZnCl
2  C 2 H 5 X  H 2O 35. Increasing order of acid strength among p-methoxyphenol,
p-methylphenol and p-nitrophenol is
the order of reactivity is
(a) p-Nitrophenol, p-Methoxyphenol, p-Methylphenol
(a) HBr > HI > HCl (b) HI > HCl > HBr
(b) p-Methylphenol, p-Methoxyphenol, p-Nitrophenol
(c) HI > HBr > HCl (d) HCl > HBr > HI (c) p-Nitrophenol, p-Methylphenol, p-Methoxyphenol
28. The best method to prepare cyclohexene from cyclohexanol (d) p-Methoxyphenol, p-Methylphenol, p-Nitrophenol
is by using
36. The correct acidic order of the following is
(a) Conc. HCl + ZnCl2 (b) Conc. H3PO4
(c) HBr (d) Conc. HCl
Properties of Phenol
29. Picric acid is
(a) Trinitrotoluene (b) Trinitroaniline
(c) A volatile liquid (d) 2, 4, 6-Trinitrophenol (a) I > II > III (b) III > II > I
30. Ortho-nitrophenol is steam volatile whereas para-nitrophenol (c) II > III > I (d) I > III > II
is not. This is due to
37. Kolbe-Schmidt reaction is used for the preparation of
(a) Intramolecular hydrogen bonding present in ortho-
nitrophenol (a) Salicylic acid (b) Salicylaldehyde
(b) Intermolecular hydrogen bonding (c) Phenol (d) Hydrocarbon
(c) Intramolecular hydrogen bonding present in para- 38. Benzenediazonium chloride on reaction with phenol in
nitrophenol weakly basic medium gives
(d) None of these (a) Diphenyl ether (b) p-hydroxyazobenzene
31. In presence of NaOH, phenol react with CHCl3 to form (c) Chlorobenzene (d) Benzene
o-hydroxy benzaldehyde. This reaction is called
(a) Reimer-Tiemann’s reaction 39.
(b) Sandmeyer’s reaction
(c) Hoffmann’s degradation reaction
(a)
(d) Gattermann’s aldehyde synthesis
32. Phenol is less acidic than (b)
(a) Acetic acid (b) p-nitrophenol
(c) Both (a) and (b) (d) None of these (c)
33. Phenol is less acidic than
(a) Ethanol (b) Methanol (d)
(c) o-nitrophenol (d) p-methylphenol
ALCOHOLS, PHENOLS AND ETHERS 271
40. Phenol reacts with bromine in carbon disulphate at low Preparation and Chemical Properties of Ethers
temperature to give which of the following product?
46. Ether is obtained from ethyl alcohol
(a) m-bromophenol (b) o-and p-bromophenol
(a) in presence of H2SO4 at 413 K
(c) p-bromophenol (d) 2,4,6-tribromophenol
(b) in presence of H2SO4 at 474 K
41. The compound ‘A’ when treated with methyl alcohol and few
drops of H2SO4 gave smell of winter green. The compound (c) in presence of H2SO4 at 383 K
‘A’ is
(d) in presence of H2SO4 at 273 K
(a) oxalic acid (b) tartaric acid
47. Product C in the following reaction, will be
(c) salicylic acid (d) succinic acid
42. With excess bromine, phenol reacts to form
(a) ethane (b) ethyl methyl ether
(c) ethyl iodide (d) propane
48. An ether is more volatile than an alcohol having the same
(a) (b) molecular formula. This is due to
(a) Dipolar character of ethers
(b) Alcohols have resonating structures
(c) Inter-molecular hydrogen bonding in ethers

(c) (d) Mixture of (a) and (b) (d) Inter-molecular hydrogen bonding in alcohols
49. The compound which does not react with sodium is
(a) C2H5OH (b)
43. Which of the following is a Reimer-Tiemann reaction? (c) CH3COOH (d)
NaOH
(a) C 6 H 5 OH  CCl 4   Salicyclic acid 50. Diethyl ether is heated with one mole of HI, which is formed
(a) Ethyl alcohol and ethyl iodide
(b) C 6 H 5 OH  Zn 
 C 6 H 6
(b) Ethyl iodide only

(c) C 6 H 5 OH  NaOH 
 C 6 H 5 ONa (c) Ethyl alcohol only
(d) Ethyl iodide and ethane
(d) None of these
51. The products formed in the following reaction
44. Which of the following reagents will produce salicylaldehyde
on reaction with phenol are
(a) CHCl3/NaOH (b) CCl4/NaOH (a)
(c) CH2Cl2/NaOH (d) CH3Cl/NaOH (b)
45. In Friedal-Crafts acylation, besides AlCl3, the other reactants are
(c)
(d) C6H6 and CH3OI
52. On boiling with concentrated hydrobromic acid, phenyl ethyl
(a) (b)
ether will yield
(a) Phenol and ethyl bromide
(b) Bromobenzene and ethanol
(c) (d) (c) Phenol and ethane
(d) Bromobenzene and ethane
ALCOHOLS, PHENOLS AND ETHERS 272
53. The ether that undergoes electrophilic substitution reactions is 58. Which of the following reaction is correctly represented
(a) CH3OC2H5 (b) C6H5OCH3
(c) CH3OCH3 (d) C2H5OC2H5
(a)
54. What is the major product of the following reaction ?

(b)

(a) (b)
(c)

(d)
(c) (d)

59. An organic compound of molecular formula C4H10O does

not react with sodium. With excess of HI, it gives only one
55. In the following reaction ‘A’ is type of alkyl halide. The compound is
(a) 1-butanol (b) ethoxyethane
(c) 1-methoxypropane (d) 2-methoxypropane
(a) C2H5CH2CHO (b) C2H5CH2CH2OH Test for Alcohols and Phenol
(c) C2H5CH2OH (d) C2H5CHO 60. Lucas test is used for
56. Which of the following product is formed, when ether is (a) Alcohols (b) Amines
exposed to air
(c) Diethyl ether (d) Glacial acetic acid
(a) Oxide (b) Alkanes
61. Lucas reagent is
(c) Alkenes (d) Peroxide of diethyl ether
(a) Conc. HCl and anhydrous ZnCl2
57. The reaction of with RMgX leads to the
(b) Conc. HNO3 and hydrous ZnCl2

formation of (c) Conc. HCl and hydrous ZnCl2

(a) RCHOHR (b) RCHOHCH3 (d) Conc. HNO3 and anhydrous ZnCl2

(c) R2CHCH2OH (d) RCH2CH2OH 62. The alcohol that produces turbidity immediately with
ZnCl 2 + conc. HCl at room temperature
(a) 1-hydroxybutane
(b) 2-hydroxybutane
(c) 2-hydroxy-2-methylpropane
(d) 1-hydroxy-2-methylpropane
63. Victor Meyer’s test is not given by
(a) (CH3)3COH (b) C2H5OH
(c) (CH3)2CHOH (d) CH3CH2CH2OH
ALCOHOLS, PHENOLS AND ETHERS 273

64. An organic compound ‘A’ reacts with methyl magnesium (B) Phenol is more acidic than benzyl alcohol
iodide, to form an addition product which on hydrolysis
forms the compound ‘B’. Compound ‘B’ gives blue colour (C) Phenoxide ion activates the ring less in
salt in Victor Meyer’s test. The compounds ‘A’ and ‘B’ are comparison to phenol
respectively
(D) Bromination of phenol in aqueous medium
(a) acetaldehyde and isopropyl alcohol
produces 2-bromophenol and 4-bromophenol.
(b) acetone and isopropyl alcohol
70. What are the number of compounds having a benzene
(c) acetaldehyde and tertiary butyl alcohol
nucleus can have the molecular formula C7H8O?
(d) acetaldehyde and ethyl alcohol
71. Find the number of products in following reaction:
Numerical Type Questions  HBr excess
Ph  O  C2 H 5  OH 

65. How many of the following option(s) is/are correct
72. A compound with molecular formula C8H18O4 does not
match?
give litmus test and does not give colour with 2,4–
(A) CH3OH – Wood alcohol
DNP. If the compounds reacts with excess MeCOCl, it
(B) C2H5OH – Grain alcohol
gives a compound whose. vapour density is 131.
Compound A contains how many hydroxy groups?
(C)
73. How many of the following compound (s)
give(s) a yellow precipitate on hypoiodite
oxidation?
(D) 2-butanol, 1-acetyl cyclopentane, ethanol and
ethanal
66. Isopropyl alcohol on treatment with excess of conc. 74. How many of the following test are used to
H2SO4 gives ‘X’ which on treatment with HBr gives distinguish 1o, 2o and 3o alcohol?
‘Y’. When ‘Y’ is dissolved in ether and treated with (A) Lucas test
sodium gives ‘Z’. Calculate the molecular weight of (B) Victor Meyer test
‘Z’. (C) KMnO4

67. Number of products formed during dehydration of the (D) Ceric ammonium nitrate test

following compounds are: 75. How many of the following reagents can be used to
bring out given transformation?
CH 3  CH 2  CH 2  OH  CH3  CH 2  CHO
(i) H  / KMnO4 / 
(ii) TsCl/DMSO + NaHCO3
(iii) PCC (Pyridinium chloro chromate)
68. The number of ether metamers represented by (iv) Bendict solution
molecular formula C4H10O is (v) Red hot Cu Tube
69. How many of the following statement(s) is/are (vi) H  / K 2 Cr2 O7 / 
correct? (vii) NBS / 
(A) o-phenolsulphonic acid can be converted into p- (viii) SeO 2 / 
phenolsulphonic acid in the presence of H2SO4 if
temperature is increased.
ALCOHOLS, PHENOLS AND ETHERS 274

EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS

1. The reaction of with HBr 4. The major product formed in the following reaction is:
(2017)
gives (2015)

(a)

(b)

(a) (b)
(c)

(d)
(c) (d)

2. Phenol, when first reacts with concentrated sulphuric acid 5. Phenol on treatment with CO2 in the presence of NaOH
and then concentrated nitric acid, gives
followed by acidification produces compound X as the
Online 2016 SET (1)
(a) o–nitrophenol (b) p–nitrophenol major product. X on treatment with (CH3CO)2O in the

(c) Nitrobenzene (d) 2, 4,6–trinitrophenol presence of catalytic amount of H2SO4 produces. (2018)

3. The increasing order of the boiling points for the following

compounds is : Online 2017 SET( 2)
C 2 H 5 OH C 2 H 5 Cl C 2 H 5 CH 3 C 2 H 5 OCH 3
(I) (II) (III) (IV) (a) (b)
(a) (III) < (IV) < (II) < (I) (b) (IV) < (III) < (I) < (II)
(c) (II) < (III) < (IV) < (I) (d) (III) < (II) < (I) < (IV)

(c) (d)
ALCOHOLS, PHENOLS AND ETHERS 275
6. The major product of the following reaction is :

Online 2018 SET (1) (a) (b)

(a) (b)
(c) (d)

10. The organic compound that gives following qualitative

analysis is:
(c) (d)
Test Inference
(a) Dil. HCl Insoluble
7. Which of the following compounds will most readily be (b) NaOH solution Soluble
dehydrated to give alkene under acidic condition ?
(c) Br2/water Decolourization
(Online 2018 SET (3)
(a) 1-Pentanol (2019-04-09/Shift-1)

(b) 4-Hydroxypentan-2-one
(c) 3-Hydroxypentan-2-one (a) (b)
(d) 2-Hydroxycyclopentanone
8. An organic compound ‘X’ showing the following solubility
profile is: (2019-04-08/Shift-1)
(c) (d)

11. The major product of the following reaction is:

(2019-04-09/Shift-2)

(a) Oleic acid (b) o – Toluidine

(c) Benzamide (d) m – Cresol
(a) (b)
9. The major product of the following reaction

(2019-04-08/Shift-1)

(c) (d)
ALCOHOLS, PHENOLS AND ETHERS 276
12. The major product of the following reaction is:

(d)
(2019-04-10/Shift-1)
15. The increasing order of pKa values of the following
compounds is (2019-01-10/Shift-1)

(a) (b)

(c) (d)
(a) C < B < A < D (b) B < C < D < A
13. What will be the major product when m-cresol is reacted (c) D < A < C < B (d) B < C < A< D
with propargyl bromide (HC  C  CH 2 Br) in presence of 16. The major product of the following reaction is :
K 2 CO3 in acetone (2019-04-12/Shift-2)

(2019-01-10/Shift-2)

(a) (b)

(a) (b)
(c) (d)

14. The products formed in the reaction of cumene with O 2

followed by treatment with dil. HCl are:
(2019-01-09/Shift-2)
(c) (d)

(a)

(b)

(c)
ALCOHOLS, PHENOLS AND ETHERS 277
17. The major product of the following reactions is: 20. The major product of the following reaction is:

(2019-01-12/Shift-2)
(2019-01-11/Shift-1)

(a) (b)
(a) (b)

(c) (d)

(c) (d)
21. The major product of the following reaction is:

18. Which of the following compounds reacts with

ethylmagnesium bromide and also decolourizes bromine
water solution: (2019-01-11/Shift-2)

(2020-09-02/Shift-2)

(a) (b)

(a) (b)

(c) (d)

(c) (d)
19.

cannot be prepared by: (2019-01-12/Shift-1)

(a) CH 3CH 2 COCH 3  PhMgX

(b) PhCOCH 2 CH 3  CH 3 MgX

(c) PhCOCH 3  CH 3CH 2 MgX

(d) HCHO  PhCH(CH 3 )CH 2 MgX

ALCOHOLS, PHENOLS AND ETHERS 278
22. Two compounds A and B with same molecular formula 24. When neopentyl alcohol is heated with an acid, it slowly
(C3H6O) undergo Grignard’s reaction with methylmagnesium converted into an 85: 15 mixture of alkenes A and B,
bromide to give products C and D. respectively. What are these alkenes?
Products C and D show following chemical tests. (2020-09-04/Shift-1)

(a)

C and D respectively are: (2020-09-02/Shift-2)

(a)

(b)

(b)

(c)
(c)

(d)

(d)

23. Consider the following reaction: 25. The major product [B] in the following reactions is:

(2020-09-04/Shift-2)
The product ‘P’ gives positive ceric ammonium nitrate
test. This is because of the presence of which of these – (a) CH 3  CH 2  CH  CH  CH 3
OH group (s) ? (2020-09-03/Shift-2)
(a) (b) only (b) (b) and (d)
(c) (c) and (d) (d) (d) only (b)

(c)

(d) CH2  CH2

ALCOHOLS, PHENOLS AND ETHERS 279
26. The major product of the following reaction is : 30. In the following reaction sequence, structures of A and B,
respectively will be:

(2020-09-05/Shift-2)

(2020-01-07/Shift-2)

(a) (b)

(a)

(c) (d)
(b)

27. The increasing order of boiling points of the following

is :

(c)

(d)

(2020-09-05/Shift-2)
31. Major product in the following reaction is:
(a) I < III < IV < II (b) III < I < II < IV

(c) I < IV < II < III (d) III < I < II < IV

28. A solution of phenol in chloroform when treated with (2020-01-08/Shift-1)

aqueous NaOH gives compound P as a major product. The
mass percentage of carbon in P is .......... (to the nearest
integer) (Atomic mass : C = 12; H = 1 ; O = 16) (a)
(2020-09-06/Shift-2)
29. 1-methyl ethylene oxide when treated with an excess of
HBr produces: (2020-01-07/Shift-1)
(b)

(a) (b)

(c) (d)
(c) (d)
ALCOHOLS, PHENOLS AND ETHERS 280
32. Arrange the following compounds in increasing order 35. What is the final product (major) ‘A’ in the given
of C—OH bond length: methanol, phenol, p-ethoxyphenol reaction? (2021-02-24 Shift-I)
(2020-01-08/Shift-1)
(a) Phenol < methanol < p-ethoxyphenol
(b) methanol < p-ethoxyphenol< phenol
(c) Phenol < p-ethoxyphenol< methanol
(d) methanol < phenol < p-ethoxyphenol
33. Find The major product [B] of the following sequence of
reactions is: (2020-01-08/Shift-2)

(a) (b)

(a)

(c) (d)

(b)
36. Which of the following compound gives pink colour on
reaction with phthalic anhydride in conc. H2SO4 followed
by treatment with NaOH? (2021-02-24-Shift-I)
(c)

(a) (b)
(d)

34. Among the following compounds A and B with molecular

formula C9H18O3, A is having higher boiling point than B.
The possible structures of A and B are: (c) (d)
(2020-01-08-Shift-2)

37. What is ‘X’ in the given reaction?

(2021-02-25/Shift-II)
(a)

CH 2 OH CH 2
(b)
(a) | (b) ||
CHO CH 2

CHO CH  OH
(c) | (d) ||
(c) CHO CH 2

(d)
ALCOHOLS, PHENOLS AND ETHERS 281
38. Given below are two statements : (2021-02-26/Shift-I)
Statement I : o-Nitrophenol is steam volatile due to
intramolecular hydrogen bonding.
(c) (d)
Statement II : o-Nitrophenol has high melting due to
hydrogen bonding.
In the light of the above statements, choose the most 42. Reaction of Grignard reagent, C2H5MgBr with C8H8O
appropriate answer from the options given below followed by hydrolysis gives compound “A” which reacts
(a) Both statement I and statement II are false instantly with Lucas reagent to give compound B, C10H13Cl.
The Compound B is: (2021-03-18-Shift-I)
(b) Statement I is false but statement II is true
(c) Statement I is true but statement II is false
(d) Both statement I and statement II are true
(a) (b)
39. Identify the major products A and B respectively in the
following reactions of phenol : (2021-02-26/Shift-I)

(c) (d)

43. Main product formed during a reaction of 1-methoxy

naphthalene with hydroiodic acid are :
(2021-03-18-Shift-II)
(a) (b)

(a) (b)

(c) (d)

(c) (d)
40. Ceric ammonium nitrate and CHCl3/alc. KOH are used for
the identification of functional groups present in _______
and _______ respectively. (2021) 44. Which of the following compounds will provide a tertiary
alcohol on reaction with excess of CH3MgBr followed by
(a) Alcohol, amine (b) Amine, phenol hydrolysis? (2021-07-22-Shift-II)
(c) Alcohol, phenol (d) Amine, alcohol
41. Identify A in the given reaction (2021-02-26-Shift-II)

(a) (b)

(c) (d)

(a) (b)
ALCOHOLS, PHENOLS AND ETHERS 282
45. An organic compound A (C6H6O) gives dark green coloration The given reaction can occur in the presence of:
with ferric chloride. On treatment with CHCl3 and KOH,
followed by acidification gives compound B. Compound B (i) Bromine water (ii) Br2 in CS2, 273 K
can also be obtained from compound C on reaction with (iii) Br2/Fe Br3 (iv) Br2 in CHCl3, 273 K
pyridinium chlorochromate (PCC). Identify A, B and C.
(2021-07-22-Shift-II) Choose the correct answer from the options given
below: (2021-07-25-Shift-I)
(a) (ii) and (iv) only

(a) (b) (i) and (iii) only

(c) (ii), (iii) and (iv) only
(d) (i), (ii) and (iv) only

(b)
48.

Consider the above reaction, the major product "P" formed

is: (2021-07-27-Shift-II)

(c)

(a) (b)

(d)
(c) (d)

(i)C2 H5 MgBr, dry ether

(ii) H2 O, HCl P
46.   (Major product)
49.
Consider the above reaction, the major product ‘P’ is:
(2021-07-25-Shift-I)
consider the above reaction, and choose the correct
statement: (2021-07-27-Shift-II)
(a) (b) (a) The reaction is not possible in acidic medium
(b) Both compounds A and B are formed equally
(c) Compound A will be the major product
(c) (d) (d) Compound B will be the major product

47.

(Major product)
ALCOHOLS, PHENOLS AND ETHERS 283
50. The correct options for the products A and B of the 52. Given below are two statements: one is labelled as:
following reactions are: (2021-08-26-Shift-II) Assertion (A) and the other is labelled as Reason (R).
Assertion (A) : Synthesis of ethyl phenyl ether may be
achieved by Williamson synthesis.
Reason (R) : Reaction of bromobenzene with sodium
ethoxide yields ethyl phenyl ether. In the light of the above
statements, choose the most appropriate answer from the
options given below (2021-08-27-Shift-I)
(a) Both (A) and (R) are correct and (R) is the correct
(a) explanation of (A)
(b) (A) is correct but (R) is not correct
(c) (A) is not correct but (R) is correct
(d) Both (A) and (R) are correct but (R) is NOT the correct
explanation of (A)
(b)
53. The major product of the following reaction, if it occurs by
SN2 mechanism is (2021-08-27-Shift-II)

(c)

(d)
(a) (b)

51. Which one of the following phenols does not give colour
when condensed with phthalic anhydride in presence of
conc. H2SO4? (2021-08-26-Shift-II)

(c) (d)

54. To synthesize 1.0 mole of 2-methylpropan-2-ol from ethyl

(a) (b) ethanoate ________ equivalents of CH3MgBr regent will
be required. (Integer value) (2021-07-20-Shift-I)

(c) (d)
ALCOHOLS, PHENOLS AND ETHERS 284

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only one correct option] 9. Phenol is heated with CCl4 and alk. KOH to form salicylic
acid. The reaction is known as:
1. , (A) is:
(a) Friedel-Crafts reaction
(b) Rosenmund reaction
(a) CH3CHO (b) CH3CH2OH (c) Reimer-Tiemann reaction
(c) H2C=CH2 (d) CH2OH–CH2OH (d) Perkin’s reaction
2. Heating together sodium ethoxide and ethyl chloride 10. Total number of isomeric alcohols with formula C4H10O
will give: is
(a) ether (b) ethyl alcohol (a) 2 (b) 1
(c) acetaldehyde (d) acetic acid (c) 3 (d) 4
3. Methyl phenyl ether can be obtained by reacting: 11. When CH3MgI is made to react with acetone and the
(a) phenolate ions and methyl iodide addition product is hydrolysed, we get:

(b) methoxide ion and bromobenzene (a) primary alcohol (b) secondary alcohol

(c) methanol and phenol (c) tertiary alcohol (d) an aldehyde

(d) bromobenzene and methyl bromide 12. To prepare propan-2-ol from methyl magnesium iodide,
the chemical reagent required is:
4. Phenol is more acidic than alcohol because:
(a) CH3CHO (b) HCHO
(a) phenol is more soluble in polar solvents
(c) CH3COCH3 (d) CO2
(b) alcohol does not lose hydrogen atom
13. Which of the following will produce a primary alcohol
(c) phenoxide ion is stabilised by resonance by reacting with CH3MgI ?
(d) phenoxide ion does not exhibit resonance (a) Ethylene oxide (b) Ethyl acetate
5. Which of the following is strongly acidic? (c) Methyl cyanide (d) Acetone
(a) Phenol (b) m-Nitrophenol 14. The major product formed in the following reaction is:
(c) m-Bromophenol (d) m-Cresol Aq. KOH
CH3CH(Cl)CH2CH2OH 
6. Phenol is less acidic than:
(a) CH3CH=CHCH2OH (b) CH2=CHCH2CH2OH
(a) p-nitrophenol (b) ethanol
(c)
(c) cresol (d) benzyl alcohol
7. Phenol on standing in air develops a red colour due to
formation of:
(d)
(a) cyclohexane (b) resorcinol
(c) phenoquinone (d) quinol
8. Phenols react with ferric chloride sodium to give:
(a) blue colouration (b) purple colouration
(c) green colouration (d) all of these
ALCOHOLS, PHENOLS AND ETHERS 285
15. Which of the following reactions will not yield alcohol 20. A compound ‘X’ undergoes reduction with LiAlH4 to
as the major product ? yield ‘Y’. When vapours of ‘Y’ are passed over freshly
reduced copper at 300oC, ‘X’ is formed. What is ‘Y’?
(a) CH3COCH3 (b) CH3CHO
(a)
(c) CH3CH2OH (d) CH3–O–CH3
21. The order of reactivity of the following alcohols towards
conc. HCl is:
(b)

(c)
(I) (II)

(d)

LiAlH4
16. CH3 COOH  (A),

(III) (IV)
H3 O
(A)  CH 3 COOH  (B)  H 2 O
(a) I > II > III > IV (b) I > III > II > IV
In the above reaction ‘A’ and ‘B’ respectively are:
(c) IV > III > II > I (d) IV > III > I > II
(a) CH3COOC2H5, C2H5OH (b) CH3CHO, C2H5OH
22. HBr reacts fastest with
(c) C2H5OH, CH3CHO (d) C2H5OH, CH3COOC2H5
(a) 2-methyl propan-2-ol (b) propan-1-ol
o
17. 300 C
The product of reaction CH3CH2OH  ? is: (c) propan-2-ol (d) 2-methyl propan-1-ol
Cu
23. The compound formed by reaction of ethylene glycol
(a) C2H6 (b) CH3COCH3 and periodic acid (HIO4) is:
(c) CH3COOH (d) CH3CHO (a) carbon dioxide (b) formic acid
18. The compound (B) formed in the following sequence of (c) formaldehyde (d) glyoxal
reactions,
(i) O 2
PClAlc.KOH 24. Cumene 
(ii) H O, H 
(X) and (Y) :
5
CH 3CH 2 CH 2 OH  (A)  (B) is : 2

(X) and (Y) respectively are:

(a) propene (b) propyne
(a) toluene, propene (b) toluene, propylchloride
(c) propane (d) propanal
(c) phenol, acetone (d) phenol, acetaldehyde
19. Identify (Z) in the series,
25. Benzene diazonium chloride on reaction with phenol in
Conc. H SO
2
C3 H 7 OH 
o
4
(X) weakly basic medium gives
170 C
(a) diphenyl ether (b) p-hydroxy azobenzene
Br2 Excess of
(X) 
(Y) 
Alc. KOH
(Z) (c) chlorobenzene (d) benzene

(a) (b) 26. Salol is prepared from:

(a) salicylic acid and methyl alcohol
(b) salicylic acid and phenol
(c) CH 3  C  CH (d)
(c) both (a) and (b)
(d) none of the above
ALCOHOLS, PHENOLS AND ETHERS 286
32. Which of the following alcohol(s) can be prepared by
the action of Grignard reagents with aldehydes?

K 2 S2 O8 (a) Primary alcohols

27. 
Heat
?
(b) Secondary alcohols
(c) Tertiary alcohols
The product formed in the reaction is:
(d) Both primary and tertiary alcohols
(a) benzoquinone (b) diphenyl ether
33. Which of the following reactions will yield Propan-2-
(c) benzene sulphuric acid (d) hydroquinone ol?
28. Phenol when condensed with phthalic anhydride in 
H
(a) H 2 C = CH  CH3  HOH 
presence of conc. H2SO4, yields:
(a) methyl orange (b) phenolphthalein 3 CH MgBr
(b) CH3  CHO 
HOH
(c) phenol red (d) salicylic acid
(i) C H MgI
29. Sodium phenoxide when heated with CO 2 under (c) CH 2 O 
2 5

(ii) HOH
pressure at 125oC gives:
(a) sodium benzoate (b) salol NeutralKMnO4
(d) H 2 C  CH  CH 3  
(c) sodium salicylate (d) salicylaldehyde
34. Diethyl ether can be distinguished from n-butanol by:
Zinc Conc. HNO3 Zn
30. Phenol 
(A) 
(B) 
distillation
(C)
Conc. H 2 SO4 NaOH
(a) aqueous FeCl3
at 60o C
(b) reaction with Na metal
In the above reaction, compounds (A), (B) and (C) are:
(c) Tollens reagent
(a) benzene, nitrobenzene and aniline
(d) reaction with CrO3 in dil H2SO4
(b) benzene, dinitrobenzene and m-nitroaniline
35. What is the function of diethyl ether in the preparation
(c) toulene, m-nitrobenzene and m-toluidine of Grignard reagent?
(d) benzene, nitrobenzene and hydrazobenzene (a) To act as a catalyst
Objection Question II (b) To act as a solvent
[One or more than one correct option] (c) To provide lone pair of electrons for coordination
31. When phenol is reacted with CHCl3 and NaOH followed
by acidification, salicylaldehyde is obtained. Which of (d) To act as an acid
the following species are involved in the above
mentioned reaction as intermediates ?
36. The ether when

treated with HI produces:

(a) (b)
(a) (b)

(c) (d)
(c) (d)
ALCOHOLS, PHENOLS AND ETHERS 287
37. Salicylic acid is prepared from phenol by: Reason (R): Phenoxide ion is more basic than ethoxide
ion.
(a) Reimer-Tiemann reaction
(a) A (b) B
(b) Kolbe’s electrolytic reaction
(c) C (d) D
(c) Kolbe’s reaction
42. Assertion (A): Phenol is more reactive than benzene
(d) none of the above towards electrophilic substitution.

38. Alcohol Reason (R): In the case of phenol, the intermediate

carbocation is more resonance stabilized.
(a) A (b) B
which is/are true about alcohol and R? (c) C (d) D
Alcohol Reagent(R) 43. Assertion (A): Alcohols can be dried over anhydrous
CaCl2.
(a) BH3/THF, H2O2/OH–
Reason (R): Anhydrous CaCl2 absorbs moisture of
aqueous ethyl alcohol

(b) Hg(OAc)2/NaBH4–H2O (a) A (b) B

(c) C (d) D
44. Assertion (A): HIO4, decomposes, 1,2-glycols but not
1,3-or higher glycols.

(c) Reason (R): Only 1,2-glycols from cyclic esters which

subsequently undergo cleavage to form carbonyl
compounds.
(a) A (b) B
(d) None of the above
(c) C (d) D
Assertion Reason
45. Assertion (A): A rate of hydrolysis of methyl chloride
(A) If both Assertion and Reason are correct and to methanol is higher in DMF than in water.
Reason is the correct explanation of Assertion.
Reason (R): Hydrolysis of methyl chloride follows
(B) If both Assertion and Reason are true but second order kinetics.
Reason is not the correct explanation of Asser-
(a) A (b) B
tion.
(C) If Assertion is true but Reason is false. (c) C (d) D
(D) If Assertion is False but reason is true. 46. Assertion (A): o-Phenol sulphonic acid on heating at
39. Assertion (A): Grignard reagent reacts with aldehydes 100oC changes to p-phenol sulphonic acid
and ketones to form alcohol. Reason (R): Sulphonation of phenol is a reversible
Reason (R): Alcohols have acidic hydrogen. process.

(a) A (b) B (a) A (b) B

(c) C (d) D (c) C (d) D

47. Assertion (A): Phenol is stronger acid than ethanol.
40. Assertion (A): Resorcinol turns FeCl3 solution purple. Reason (R): Group with + M effect and -I effect decrease
Reason (R): Resorcinol have phenolic group. acidity at m-position.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
41. Assertion (A): Phenol undergo Kolbe reaction, ethanol
does not.
ALCOHOLS, PHENOLS AND ETHERS 288

Match the Following

Each question has two columns. Four options are
given representing matching of elements from
Column-I and Column- II. Only one of these four
options corresponds to a correct matching.For
each question, choose the option corresponding
to the correct matching.
48. Match the following :
Column-I Column-II
(Compound) (Possible reaction)
Answer the following questions:
49. Which among the following alcohols will be the most
reactive for dehydration?

(A) (P) Reaction with NaOH

(a)

(b)

(B) (Q) Reaction with NaHCO3

(c)

(C) CH3COOH (R) Reaction with PCl5

(d)
(D) C2H5OH (S) Reaction with NH3
50. Arrange the reactivity of given four alcohols in
Paragraph Type Questions decreasing order of dehydration.
Use the following passage, solve Q. 49 to Q. 52
Passage
Secondary and tertiary alcohols always gives E 1
reaction in dehydration. Primary, alcohols whose -car-
o o
bon is 3 or 4 also give E1 reaction. However, the pri-
o o
mary alcohols whose -carbon is 1 or 2 give E2 reac-
tion. Dehydrating agents like conc. H2SO4, Al2O3, an-
hydrous ZnCl2 are used.
The reactivity of alcohols for elimination reaction lies
in following sequence:
Tertiary alcohol > secondary alcohol > primary alcohol
Electron attracting groups present in alcohols decrease
the reactivity for dehydration. Greater is the –I effect of
the group present in alcohol, less will be its reactivity.
Both E1 and E2 mechanism give the product according (a) A > B > C > D (b) D > C > B > A
to Saytzeff’s rule, i.e., major product is the most substi- (c) A > D > B > C (d) B > C > A > D
tuted alkene
ALCOHOLS, PHENOLS AND ETHERS 289
53. Which of the following reagents when heated will give
a good yield of an ether
51. In the reaction, the
(a) Isopropyl bromide and sodium isopropoxide
(b) Isopropyl bromide and sodium ethoxide
product(s) obtained will be:
(c) Bromobenzene and sodium phenoxide
(a)
(d) Sodium tert-butoxide and ethyl bromide
54. Which of the following ethers can be prepared by
(b) Willamson synthesis ?
(a) Benzyl methyl ether (b) Methyl vinyl ether
(c) Divinyl ether (d) Diphenyl ether
55. Allyl phenyl ether can be prepared by heating
(c)
(a) C6H5Br + CH2 = CH—CH2ONa
(d) this alcohol cannot be dehydrated (b) CH2 = CHCH2 Br + C6H5ONa
52. Which among the following sequences of reactivity for (c) C6H5CH = CHBr + CH3ONa
dehydration is incorrect?
(d) CH2 = CHBr + C6H5CH2ONa
56. Benzyl ethyl ether reacts with HI to form
(a) p-Iodotoluene and ethyl alcohol
(a)
(b) Benzyl alcohol and ethyl iodide
(c) Benzyl iodide and ethyl alcohol
(d) Iodobenzene and ethyl alcohol

Subjective Type Questions

(b)
57. Write down the main product of the following reaction :

58. How may be the following transformation be carried out (in

not more than six steps) ?
(c)
“Ethyl alcohol to vinyl acetate.”
59. An optically active alcohol A (C6H10O) absorbs two moles
of hydrogen per mole of A upon catalytic hydrogenation
(d) and gives a product B. The compound B is resistant to
oxidation by CrO3 and does not show any optical activity.
Use the following passage, solve Q. 53 to Q. 56 Deduce the structure of A and B.
Passage 60. An organic liquid ‘A’ containing C, H and O with boiling
By a proper choice of reagents, both symmetrical and point 78ºC, possessing a rather pleasant odour, on heating
unsymmetrical ethers can be prepared by Williamson with concentrated sulphuric acid gives a gaseous product
synthesis which involves the reaction between an alkyl ‘B’ with the empirical formula, CH2. ‘B’ decolourises bromine
halide and an alkoxide ion. The reverse process water as well as alkaline permanganate solution and takes
up one mole of H2 (per mole of B) in presence of finely
involving the cleavage of ethers to give back the original
divided nickel at high temperature. Identify the substances
alkyl halide and the alcohol can be carried out by heating
A and B.
the ether with HI at 373 K.
ALCOHOLS, PHENOLS AND ETHERS 290
61. 3, 3-dimethylbutan-2-ol losses a molecule of water in the 67. An alcohol A, when heated with conc. H2SO4 gives an alkene
presence of concentrated sulphuric acid to give B. When B is bubbled through bromine water and the
tetramethylethylene as a major product. Suggest a suitable product obtained is dehydrohalogenated with excess of
mecahnism. sodamide, a new compound C is obtained. The compound C
gives D when treated with warm dilute H2SO4 in presence of
62. Give reasons for the following in one or two sentences.
HgSO4. D can also be obtained either by oxidising A with
“Acid catalysed dehydration of t-butanol is faster than that KMnO4 or from acetic acid through its calcium salt. Identify
of n-butanol.” A, B, C and D.

63. Which of the following is the correct method for synthesizing 68. Compound X (molecular formula, C5H8O) does not react
methyl-t-butyl ether and why ? appreciably with Lucas reagent at room temperature but gives
a precipitate with ammoniacal silver nitrate. With excess of
(i) (CH3)3CBr + NaOMe MeMgBr, 0.42 g of X gives 224 mL of CH4 at STP. Treatment
(ii) CH3Br + NaO-t-Bu of X with H2 in presence of Pt catalyst followed by boiling
with excess HI, gives n-pentane. Suggest structure for X
64. A compound ‘X’ containing C, H and O is unreactive towards and write the equation involved.
sodium. It does not add with bromine. It also does not react
with Schiff’s reagent. On refluxing with an excess of HI, ‘X’ 69. Explain briefly the formation of products giving the
yields only one organic product ‘Y’. ‘Y’ on hydrolysis yields structures of the intermediates.
a new compound ‘Z’ which can be converted into ‘Y’ by
reaction with red phosphorus and iodine. The compound (a) (i)
‘Z’ on oxidation with potassium permanganate gives a
carboxylic acid. The equivalent weight of acid is 60. What
are the compounds ‘X’, ‘Y’ and ‘Z’ ? Write chemical
equations leading to the conversion of ‘X’ to ‘Y’.

65. 2, 2-dimethyloxirane can be cleaved by acid (H ). Write
mechanism. (ii)
66. Indicate steps which would convert :

(i) phenol to acetophenone 70. A compound of molecular formula C7H8O is insoluble in

water and dilute sodium bicarbonate but dissolves in dilute
(ii) acetic acid to tert-butyl alcohol
aqueous sodium hydroxide and gives a characteristic colour
with aqueous FeCl3. On treatment with bromine water, it
readily gives a precipitate of C7H5OBr3. Write down the
structure of the compound.
ALCOHOLS, PHENOLS AND ETHERS 291

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

Objective Questions I
[Only one correct option]
1. Which one of the following will most readily be dehydrated 5.
in acidic condition ? (2000)

How many structures of F is possible ? (2003)

(a) (b)
(a) 2 (b) 5
(c) 6 (d) 3
6. When phenyl magnesium bromide reacts with tert. butanol,
which of the following is formed ? (2005)
(c) (d)
(a) Tert. butyl methyl ether
(b) Benzene
2. 1-propanol and 2-propanol can be best distinguished by
(2001) (c) Tert. butyl benzene
(a) oxidation with alkaline KMnO4 followed by reaction with (d) Phenol
Fehling solution
7. The best method to prepare cyclohexene from cyclohexanol
(b) oxidation with acidic dichromate followed by reaction is by using (2005)
with Fehling solution
(a) conc. HCl + ZnCl2 (b) conc. H3PO4
(c) oxidation by heating with copper followed by reaction
with Fehling solution (c) HBr (d) conc. HCl

(d) oxidation with concentrated H2SO4 followed by reaction 8. (I) 1, 2-dihydroxy benzene (2006)
with Fehling solution (II) 1, 3-dihydroxy benzene
3. The compound that will react most readily with NaOH to (III) 1, 4-dihydroxy benzene
form methanol is (2001)
(IV) Hydroxy benzene
(a) (b) CH3OCH3
The increasing order of boiling points of above mentioned
alcohols is
(c) (d) (CH3)3CI
(a) I < II < III < IV (b) I < II < IV < III
4. Compound ‘A’ (molecular formula C3H8O) is treated with
acidified potassium dichromate to form a product ‘B’ (c) IV < I < II < III (d) IV < II < I < III
(molecular formula C3H6O) ‘B’ forms a shining silver mirror
on warming with ammoniacal silver nitrate. ‘B’ when treated
with an aqueous solution of H2NCONHNH2 and sodium
acetate gives a product ‘C’. Identify the structure of ‘C’.
(2002)
(a) CH3CH2CH NNHCONH2
(b)

(c)

(d) CH3CH2OH + NCONHNH2

ALCOHOLS, PHENOLS AND ETHERS 292
9. The acidic hydrolysis of ether (X) shown below is fastest
when (2014)

(a)

(b)

(a) one phenyl group is replaced by a methyl group.

(b) one phenyl group is replaced by a para-methoxphenyl
group.
(c) Two phenyl groups are replaced by two
para-methoxyphenyl groups.
(d) no structural change is made of X. (c)

Objective Questions II
[One or more than one correct option]
10. The correct combination of names for isomeric alcohols with
molecular formula C4H10O is/are (2014)
(a) tert-butanol and 2-methylpropan-2-ol
(d)
(b) tert-butanol and 1, 1-dimethylethan-1-o1
(c) n-butanol and butan1-ol
Numeric Value Type Questions
(d) isobutyl alcohol and 2-methylpropan 1-ol
13. The number of resonance structures for N is (2015)
11. Among the following reactions(s) which gives(give)
tert-butyl benzene as the major product is(are) (2016)

(a) (b)

14. An organic compound (C8 H10 O 2 ) rotates plane-

(c) (d) polarized light. It produces pinkcolor with neutral
FeCl3 solution. What is the total number of all the
12. Choose the correct option(s) for the following set of possible isomers for this compound?
reactions (2020/Shift-2)

(2019/Shift-1)
ALCOHOLS, PHENOLS AND ETHERS 293
Assertion Reason
(A) If both assertion and reason are correct and
reason is the correct explanation of assertion.
(B) If both assertion and reason are true but
reason is not the correct explanation of
assertion.
(C) If assertion is true but reason is false.
(D) If assertion is false but reason is true.

15. Assertion : Bromobenzene, upon reaction with Br2/Fe gives

1, 4-dibromobenzene as the major product.

Reason : In bromobenzene, the inductive effect of the

bromo group is more dominant than the
mesomeric effect in directing the incoming
electrophile. (2008)
The correct option is (2018)
Match the Following (a) P - 1; Q - 2,3; R - 1, 4; S - 2, 4
(b) P - 1, 5; Q - 3,4; R - 4, 5; S - 3
Each question has two columns. Four options are (c) P - 1,5; Q - 3,4; R - 5; S - 2, 4
given representing matching of elements from Col- (d) P - 1, 5; Q - 2, 3; R - 1,5; S - 2, 3

umn-I and ColumnII. Only one of these four options Paragraph Type Questions
corresponds to a correct matching.For each ques- Use the following passage, to anwers Q.17 to Q.19
tion, choose the option corresponding to the cor- Passage
Reimer-Tiemann reaction introduces an aldehyde group, on
rect matching.
to the aromatic ring of phenol, ortho to the hydroxyl group.
16. The desired product X can be prepared by reacting the major This reaction involves electrophilic aromatic substitution.
product of the reaction in List-I with one or more appropriate This is a general method for the synthesis of substituted
reagents in List-II salicylaldehydes as depicted below : (2007)
(given, order of migratory aptitude : ary1 > alkyl > hydrogen)
ALCOHOLS, PHENOLS AND ETHERS 294
17. Which one of the following reagents is used in the above 20. Compound H is formed by the reaction of
reaction ?
(a) aq. NaOH + CH3Cl
(a)
(b) aq. NaOH + CH2Cl2
(c) aq. NaOH + CHCl3
(d) aq. NaOH + CCl4
(b)
18. The electrophile in this reaction is
(a) : CHCl (b) CHCl2
(c) : CCl2 (d) • CCl3 (c)
19. The structure of the intermediate I is

(d)

(a) (b) 21. The structure of compound I is

(a) (b)

(c) (d)
(c) (d)

22. The structures of compounds J, K and L respectively, are

(a) PhCOCH3, PhCH2COCH3 and PhCH2COO–K+
(b) PhCHO, PhCH2CHO and PhCH2COO–K+
Use the following passage, to anwers Q.20 to Q.22 (c) PhCOCH3, PhCH2CHO and CH3COO–K+
Passage
(d) PhCHO, PhCOCH3 and PhCOO–K+
A tertiary alcohol H upon acid catalysed dehydration gives
a product I. Ozonolysis of I leads to compounds J and K. Subjective Type Questions
Compound J upon reaction with KOH gives benzyl alcohol
and a compound L, where K on reaction with KOH gives 23. Cyclobutylbromide on treatment with magnesium in dry ether
only M. forms an organometallic compound (A). The organometallic
reacts with ethanal to give an alcohol (B) after mild
acidification. Prolonged treatment of alcohol (B) with an
equivalent amount of HBr gives 1-bromo-1-
methylcyclopentane (C). Write the structures of (A), (B) and
explain how (C) is obtained from (B). (2001)
(2008)
ALCOHOLS, PHENOLS AND ETHERS 295
24. An organic compound ‘P’ having the molecular formula
C5H10O when treated with dil H2SO4 gives two compounds,
Q & R both gives positive iodoform test. The reaction of
25.
C5H10O with dil H2SO4 gives reaction 1015 times faster than
ethylene. Identify organic compound of Q and R. Give the
reason for the extra stability of P. (2004)

Identify X and Y. (2005)

ALCOHOLS, PHENOLS AND ETHERS 296

Note:

Find Answer Key and Detailed Solutions at the end of this book

ALCOHOLS, PHENOLS
AND ETHERS
Please share your valuable feedback by
scanning the QR code.
ANSWER KEY 297

Answer Key
CHAPTER -1 SOLUTIONS

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (a) 2. (d) 3. (a) 4. (a) 5. (a) 1. (b) 2. (b) 3. (c) 4. (c) 5. (c)
6. (b) 7. (c) 8. (b) 9. (b) 10. (a) 6. (c) 7. (b) 8. (b) 9. (c) 10. (a)
11. (a) 12. (d) 13. (b) 14. (c) 15. (c) 11. (a) 12. (b) 13. (b) 14. (c) 15. (d)
16. (c) 17. (c) 18. (d) 19. (c) 20. (c) 16. (c) 17. (c) 18. (c) 19. (a) 20. (c)
21. (a) 22. (c) 23. (b) 24. (c) 25. (d) 21. (b) 22. (b) 23. (b) 24. (a) 25. (a)
26. (a) 27. (d) 28. (a) 29. (a) 30. (d) 26. (c) 27. (d) 28. (c) 29. (b) 30. (a)
31. (47.00) 32. (d) 33. (177.0) 34. (600)
31. (c) 32. (b) 33. (a) 34. (a) 35. (c)
36. (d) 37. (c) 38. (b) 39. (b) 40. (d) 35. (167.0) 36. (d) 37. (5.00) 38. (d)
39. (d) 40. (b) 41. (c) 42. (14.00) 43. (1.76)
41. (b) 42. (a) 43. (a) 44. (b) 45. (b)
44. (10.00) 45. (2.00) 46. (36.00) 47. (1.00)
46. (a) 47. (a) 48. (a) 49. (b) 50. (a)
48. (375.0) 49. (3.00) 50. (24.00) 51. (2.00)
51. (b) 52. (b) 53. (a) 54. (c) 55. (a) 52. (9.00) 53. (106) 54. (19.00) 55. (25.00)
56. (d) 57. (d) 58. (c) 59. (b) 60. (a) 56. (64.00) 57. (85.00) 58.
61. (d) 62. (a) 63. (40.00mL) (50.00) 59. (1.00) 60. (78.00) 61. (1.00)
64. (0.01M) 65. (93.00g) 62. (25.01) 63. (250) 64. (125) 65. (15.00)
66. (210.0g mol ) 67. (0.156)68. (0.086) 69.
-1 66. (4.00)67. (3.00) 68. (269.0) 69. (518.0)
(350.0) 70. (2.28 mol kg-1) 71. (2.05M) 72. (1.22) 70. (271.0) 71. ( 13 102 ) 72. (a)
73. (-0.480oC) 74. (0.0558K) 75. (50.00) 73. (d) 74. (a) 75. (d)
ANSWER KEY 298

CHAPTER -1 SOLUTIONS

EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

DIRECTION TO USE -
DIRECTION TO USE -
Scan the QR code and check detailed solutions.
Scan the QR code and check detailed solutions.

1. (a) 2. (b) 3. (b) 4. (a) 5. (a) 1. (0.228K)2. (a) 4. (a) 5. (122;244)

6. (c) 7. (c) 8. (c) 9. (b) 10. (a) 6. (a) 7. (75) 8. (a) 9. (d)
11. (b) 12. (a) 13. (c) 14. (b) 15. (b) 10. (b) 11. (b) 12. (a) 13. (a)
16. (c) 17. (c) 18. (c) 19. (c) 20. (b) 14. (a) 15. (8.00) 16. (b,c,d) 17. (19.00)
21. (d) 22. (c) 23. (b) 24. (d) 25. (c) 18. (a,b) 19. (c) 20. (1.02) 21. (2.98)
26. (b) 27. (b) 28. (c) 29. (d) 30. (b) 22. (0.11) 23. (0.20) 24. (100.1) 25. (2.50)
31. (c) 32. (a) 33. (c) 34. (c) 35. (b)
36. (d) 37. (a) 38. (c) 39. (c) 40. (c)
41. (b) 42. (d) 43. (d) 44. (b) 45. (a)
46. (b) 47. (c) 48. (c) 49. (c) 50. (a)
51. (c) 52. (a) 53. (a) 54. (a) 55. (c)
56. (a) 57. (a) 58. (a,c) 59. (b,d) 60. (b,d)
61. (b,d) 62. (a,b,c,d) 63. (a,d) 64. (a,b,d)
65. (b,c) 66. (c,d) 67. (34.00)
68. (85.00) 69. (15.7%) 70. (b)
71. (a) 72. (b) 73. (a) 74. (b) 75. (a)
76. (A–R,S; B–R; C–P; D–Q)
77. (A–R,S; B–P,Q; C–R,S; D–P,Q)
78. (d) 79. (d) 80. (a)
ANSWER KEY 299

CHAPTER -2 SOLID STATE

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (d) 2. (c) 3. (d) 4. (a) 5. (d) 1. (c) 2. (a) 3. (b) 4. (c) 5. (a)
6. (a) 7. (d) 8. (b) 9. (d) 10. (b) 6. (c) 7. (d) 8. (b) 9. (a) 10. (c)
11. (a) 12. (b) 13. (c) 14. (b) 15. (b) 11. (a) 12. (a) 13. (d) 14. (a) 15. (c)
16. (d) 17. (c) 18. (a) 19. (c) 20. (d) 16. (c) 17. (d) 18. (143.0) 19. (d) 20. (d)
21. (a) 22. (8.00) 23. (9076)24. (1.00) 25. (33.00)
21. (d) 22. (b) 23. (b) 24. (c) 25. (a)
26. (15.00) 27. (5.00) 28. (8.00) 29. (106.0)
26. (d) 27. (b) 28. (a) 29. (d) 30. (b)
30. (1.00) 31. (b) 32. (a) 33. (d) 34. (c)
31. (d) 32. (d) 33. (c) 34. (c) 35. (c)
35. (c)
36. (b) 37. (b) 38. (a) 39. (b) 40. (b)
41. (b) 42. (c) 43. (d) 44. (c) 45. (b)
46. (c) 47. (c) 48. (a) 49. (c) 50. (d)
51. (d) 52. (b) 53. (a) 54. (b) 55. (c)
56. (b) 57. (b) 58. (b) 59. (a) 60. (b)
61. (d) 62. (b) 63. (1.85 × 10-8) 64. (0.91)
65. (4.00)66. (8.96)67. (2.00) 68. (5.18) 69. (2.16)
70. (152.0) 71. (128.0) 72. (0.5 × 1025) 73.
(4.08) 74. (26.00) 75. (2.57 x 1021)
ANSWER KEY 300

CHAPTER -2 SOLID STATE

EXERCISE - 4 :
EXERCISE - 3 :
PREVIOUS YEAR JEE ADVANCED QUESTIONS
ADVANCED OBJECTIVE QUESTIONS

DIRECTION TO USE -
DIRECTION TO USE -
Scan the QR code and check detailed solutions.
Scan the QR code and check detailed solutions.

1. (d) 3. (117 pm) 4. (b)

1. (b) 2. (c) 3. (d) 4. (c) 5. (b)
6. (c) 7. (d) 8. (a) 9. (a) 10. (c) 5. (217 pm)6. (A - p, s ; B - p, q ; C - q ; D - q, r)
11. (b) 12. (b) 13. (a) 14. (a) 15. (c) 7. (b) 8. (a) 9. (d) 10. (a)
16. (c) 17. (b) 18. (c) 19. (a) 20. (c) 11. (b,c,d) 12. (2.00) 13. (3.00) 14. (a,c)
15. (b)
21. (b) 22. (b) 23. (c) 24. (c) 25. (d)
26. (c) 27. (b) 28. (d) 29. (d) 30. (c)
31. (d) 32. (d) 33. (b) 34. (a) 35. (a)
36. (b,c,d) 37. (a,d) 38. (a,b) 39. (a,b,c)
40. (a,d) 41. (a,b) 42. (b,d) 43. (a,b) 44. (a,c)
45. (a,c,d) 46. (b,c) 47. (a,c)
48. (1.86A) 49. (1.26) 50. (4.00) 51. (5.00)
52. (7.00) 53. (6) 54. (124.3 pm, 7.3) 55. (6.00)
56. (8.00)57. (3.00) 58. (c) 59. (a) 60. (b)
61. (d) 62. (d) 63. (b) 64. (d) 65. (d)
66. (c) 67. (c) 68. (a)
69. (A - (p, r, s); B - ( r); C - (q); D - (r))
70. (A - (r); B - (s); C - (p, s); D - (q))
71. (b) 72. (b) 73. (c) 74. (c) 75. (a)
76. (b) 77. (d) 78. (a) 79. (c) 80. (a)
ANSWER KEY 301
CHAPTER -3 GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (a) 2. (b) 3. (b) 4. (b) 5. (b) 1. (d) 2. (d) 3. (d) 4. (c) 5. (b)
6. (d) 7. (a) 8. (d) 9. (d) 10. (a) 6. (d) 7. (a) 8. (b) 9. (c) 10. (b)
11. (d) 12. (d) 13. (d) 14. (a) 15. (d) 11. (a) 12. (c) 13. (c) 14. (b) 15. (d)
16. (d) 17. (a) 18. (d) 19. (b) 20. (a) 16. (c) 17. (b) 18. (c) 19. (a,b) 20. (a)
21. (c) 22. (b) 23. (d) 24. (d) 25. (c) 21. (b) 22. (a) 23. (b) 24. (b) 25. (c)
26. (b) 27. (c) 28. (d) 29. (c) 30. (d) 26. (d) 27. (d) 28. (c) 29. (a) 30. (d)
31. (d) 32. (a) 33. (c) 34. (b) 35. (d) 31. (c) 32. (a) 33. (c) 34. (d) 35. (c)
36. (c) 37. (d) 38. (b) 39. (d) 40. (c) 36. (5.00)37. (6.00) 38. (10.00)
41. (a) 42. (a) 43. (a) 44. (a) 45. (a) 39. (60.00) 40. (b) 41. (c) 42. (d)
46. (c) 47. (a) 48. (c) 49. (c) 50. (c) 43. (d) 44. (a,d) 45. (a)
51. (c) 52. (d) 53. (b) 54. (d) 55. (d)
56. (c) 57. (c) 58. (c) 59. (c) 60. (c)
61. (c) 62. (c) 63. (b) 64. (b) 65. (d)
66. (b) 67. (b) 68. (a) 69. (c) 70. (c)
71. (a) 72. (b) 73. (c) 74. (a) 75. (c)
76. (c) 77. (a) 78. (d) 79. (d) 80. (b)
81. (d) 82. (d) 83. (d) 84. (a) 85. (c)
86. (d) 87. (c) 88. (c) 89. (c) 90. (c)
91. (b) 92. (a) 93. (a) 94. (c) 95. (b)
96. (b) 97. (d) 98. (d) 99. (d) 100. (b)
101. (d) 102. (c) 103. (b) 104. (c) 105. (b)
106.(c) 107. (b) 108. (a) 109. (c) 110. (a)
111. (c) 112. (a) 113. (c) 114. (c) 115. (d)
116. (c) 117. (d) 118. (d) 119. (d) 120. (c)
121. (b) 122. (d) 123. (a) 124. (c) 125. (b)
126. (b) 127. (b) 128. (c) 129. (b) 130. (a)
ANSWER KEY 302

CHAPTER -3 GENERAL ORGANIC CHEMISTRY (REVISION) & ISOMERISM

EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (b) 2. (d) 3. (a) 4. (a) 1. (d) 2. (d) 3. (c) 4. (a)

5. (d) 6. (c) 7. (d) 8. (c) 5. (c) 6. (b) 7. (a) 8. (c)
9. (d) 10. (d) 11. (b) 12. (a) 9. (c) 10. (b) 11. (a,d) 12. (b,c,d)
13. (a) 14. (a) 15. (a) 16. (b) 13. (a,d) 14. (a,c) 15. (a,b,c) 16. (c,d)
17. (a) 18. (b) 19. (c) 20. (c) 17. (7.00) 18. (10.00)
21. (b) 22. (c) 23. (b) 24. (b)
25. (c) 26. (c) 27. (c) 28. (c)
29. (b) 30. (c) 31. (b) 32. (a)
33. (b) 34. (a) 35. (b) 36. (c)
37. (a) 38. (d) 39. (a,d) 40. (a,b)
41. (c,d) 42. (b,d) 43. (b,c) 44. (a,c,d)
45. (b,c,d) 46. (a,b,d) 47. (c,d) 48. (a,b)
49. (a,b) 50. (b,d) 51. (c,d) 52. (c,d)
53. (a,d) 54. (a,b,d) 55. (a,c,d) 56. (a,b,d)
57. (a,b,d) 58. (c,d) 59. (a,c) 60. (a,b,c,d)
61. (3.00) 62. (8.00) 63. (621.0) 64. (4.00)
65. (6.00) 66. (4.00) 67. (64.00) 68. (2341)
69. (b) 70. (b) 71. (a) 72. (c)
73. (d) 74. (a) 75. (a) 76. (a)
77. (a) 78. (A-q, B-r, C-s, D-p)
79. (A-q, B-q,r, C-p,q, D-s)
80. (A-p,r, B-q,s, C-p,q,r, D-p)
81. (A-p,q,r,s; B-p,q,s; C-p,s; D-p)
82. (A-r; B-p; C-q; D-q)
83. (a) 84. (c) 85. (c) 86. (a)
87. (d) 88. (b) 89. (c) 90. (c)
91. (a) 92. (c) 93. (b) 94. (b)
98. (non-superimposable, enantiomers)
99. (Cyclopropane) 100. (Butanedioic acid.)
ANSWER KEY 303

CHAPTER -4 ALKYL AND ARYL HALIDES

EXERCISE - 1 :
BASIC OBJECTIVE QUESTIONS

DIRECTION TO USE -
Scan the QR code and check detailed solutions.

1. (a) 2. (d) 3. (d) 4. (a) 81. (a) 82. (b) 83. (b) 84. (b)
5. (b) 6. (c) 7. (b) 8. (b) 85. (b) 86. (a) 87. (a) 88. (b)
9. (c) 10. (a) 11. (c) 12. (d) 89. (c) 90. (b) 91. (a) 92. (d)
13. (a) 14. (a) 15. (a) 16. (b) 93. (a) 94. (a) 95. (c) 96. (d)
17. (b) 18. (a) 19. (a) 20. (b) 97. (c) 98. (b) 99. (c) 100. (a)
21. (b) 22. (d) 23. (a) 24. (c) 101. (a) 102. (d) 103.(a) 104. (c)
25. (b) 26. (a) 27. (d) 28. (c) 105. (a) 106. (a) 107. (b) 108. (a)
29. (b) 30. (c) 31. (c) 32. (c) 109. (d) 110. (d) 111. (c) 112. (b)
33. (b) 34. (d) 35. (c) 36. (c) 113. (a) 114. (d) 115. (b) 116. (b)
37. (d) 38. (d) 39. (a) 40. (a) 117. (a) 118. (a) 119. (b) 120. (d)
41. (d) 42. (b) 43. (c) 44. (a) 121. (d) 122. (c) 123. (a) 124. (a)
45. (d) 46. (c) 47. (d) 48. (d) 125. (c) 126. (b) 127. (b) 128. (b)
49. (a) 50. (d) 51. (b) 52. (b) 129. (b) 130. (a) 131. (b) 132. (a)
53. (c) 54. (b) 55. (a) 56. (b) 133. (c) 134. (b) 135. (c) 136. (c)
57. (c) 58. (a) 59. (b) 60. (b) 137. (b) 138. (a) 139. (c) 140. (3.00)
61. (a) 62. (b) 63. (d) 64. (c) 141. (3.00) 142. (2.00) 143. (0.00) 144. (73.00)
65. (b) 66. (a) 67. (d) 68. (c) 145. (4.00) 146. (4.00) 147. (3.00) 148. (4.00)
69. (c) 70. (a) 71. (d) 72. (b) 149. (4.00) 150. (3.00)
73. (a) 74. (a) 75. (d) 76. (d)
77. (c) 78. (a) 79. (d) 80. (a)
ANSWER KEY 304

CHAPTER -4 ALKYL AND ARYL HALIDES

EXERCISE - 2 : EXERCISE - 3 :
PREVIOUS YEAR JEE MAIN QUESTIONS ADVANCED OBJECTIVE QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (d) 2. (a) 3. (a) 4. (b) 1. (b) 2. (b) 3. (d) 4. (a)

5. (b) 6. (d) 7. (a) 8. (b) 5. (d) 6. (b) 7. (d) 8. (a)
9. (d) 10. (b) 11. (b) 12. (d) 9. (d) 10. (c) 11. (a) 12. (a)
13. (d) 14. (b) 15. (b) 16. (a) 13. (b) 14. (b) 15. (b) 16. (c)
17. (a) 18. (a) 19. (b) 20. (a) 17. (c) 18. (b) 19. (c) 20. (a)
21. (a) 22. (a) 23. (b) 24. (c) 21. (c) 22. (b) 23. (a) 24. (c)
25. (d) 26. (d) 27. (d) 28. (c) 25. (c) 26. (d) 27. (d) 28. (b)
29. (d) 30. (b) 31. (d) 32. (a) 29. (a) 30. (d) 31. (b) 32. (b)
33. (c) 34. (d) 35. (b) 36. (a) 33. (d) 34. (d) 35. (c) 36. (b)
37. (b) 38. (b) 39. (d) 40. (a) 37. (a) 38. (b) 39. (c) 40. (d)
41. (d) 42. (a) 43. (c) 44. (d) 41. (a) 42. (c) 43. (a) 44. (b)
45. (d) 45. (d) 46. (c) 47. (a) 48. (c)
49. (a,c,d) 50. (a,b) 51. (b,c,d) 52. (a,b,d)
53. (c,d) 54. (a,b,c,d) 55. (a,b,c) 56. (a,b,c)
57. (b,c,d) 58. (a,c,d) 59. (a,b) 60. (a,b,d)
61. (a,b,d) 62. (b,c) 63. (b,c,d) 64. (b,d)
65. (a,c,d) 66. (a,c,d) 67. (a,b) 68. (a,b,c,d)
69. (6.00) 70. (4.00) 71. (4.00) 72. (3.00)
73. (4.00) 74. (4.00) 75. (3.00) 76. (8.00)
77. (d) 78. (a) 79. (d) 80. (b)
81. (b) 82. (a) 83. (a) 84. (a)
85. (d) 86. (a) 87. (c) 88. (a)
89. (c) 90. (c) 91. (d) 92. (a)
93. (b) 94. (b) 95. (c) 96. (a)
97. (a)
98. (A-q, B-s, C-p, D-r) 99. (A-q, B-s, C-p, D-r)
100. (A-s, B-r, C-q, D-r) 101. (A-s, B-r, C-p, D-q)
102. (A-q,r, B-q,r, C-p, D-s)103.(A-r,s, B-s, C-q, D-p)
104. (A-r,s, B-r,s, C-p,r, D-p,q)
105. (A-p,q,r, B-p,r, C-p,s, D-p,r)
106. (a) 107. (c) 108. (b) 109. (c)
110. (a) 111. (b) 112. (d) 113. (d)
114. (a) 115. (c) 116. (a) 117. (d)
118. (a) 119.(b) 120. (d)
ANSWER KEY 305

CHAPTER -4 ALKYL AND ARYL HALIDES

EXERCISE - 4 :
PREVIOUS YEAR JEE ADVANCED QUESTIONS

DIRECTION TO USE -
Scan the QR code and check detailed solutions.

1. (c) 2. (d) 3. (d) 6. (d)

8. (b) 9. (d) 10. (b) 11. (a)
13. (a) 14. (a) 15. (a) 16. (b,d)
17. (b) 18. (13.00) 19. (a) 20. (d)
ANSWER KEY 306
CHAPTER -5 ALCOHOLS, PHENOLS AND ETHERS

EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (b) 2. (a) 3. (b) 4. (c) 5. (d) 1. (b) 2. (d) 3. (a) 4. (a) 5. (b)
6. (d) 7. (c) 8. (d) 9. (c) 10. (c) 6. (b) 7. (b) 8. (d) 9. (d) 10. (b)
11. (d) 12. (a) 13. (a) 14. (c) 15. (d) 11. (c) 12. (c) 13. (c) 14. (c) 15. (d)
16. (b) 17. (a) 18. (b) 19. (c) 20. (a)
16. (b) 17. (a) 18. (d) 19. (d) 20. (b)
21. (c) 22. (d) 23. (b) 24. (a) 25. (b)
21. (c) 22. (b) 23. (a) 24. (c) 25. (c)
26. (d) 27. (c) 28. (b) 29. (d) 30. (a)
31. (a) 32. (c) 33. (c) 34. (c) 35. (d) 26. (c) 27. (c) 28. (68.85%)29. (c) 30. (a)
36. (b) 37. (a) 38. (b) 39. (a) 40. (b) 31. (c) 32. (c) 33. (c) 34. (b) 35. (d)
41. (c) 42. (c) 43. (a) 44. (a) 45. (b) 36. (d) 37. (b) 38. (c) 39. (d) 40. (a)
46. (a) 47. (b) 48. (d) 49. (b) 50. (a) 41. (c) 42. (c) 43. (b) 44. (a) 45. (a)
51. (b) 52. (a) 53. (b) 54. (d) 55. (b) 46. (c) 47. (c) 48. (b) 49. (c) 50. (b)
56. (d) 57. (d) 58. (a) 59. (b) 60. (a) 51. (b) 52. (b) 53. (d) 54. (2.00)
61. (a) 62. (c) 63. (a) 64. (a) 65. (4.00)
66. (86.00) 67. (4.00) 68. (3.00) 69. (2.00)
70. (5.00) 71. (2.00) 72. (2.00) 73. (4.00)
74. (3.00) 75. (4.00)
ANSWER KEY 307
CHAPTER -5 ALCOHOLS, PHENOLS AND ETHERS

EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1.(b) 2.(a) 3.(a) 4.(c) 1. (a) 2. (c) 3. (a) 4. (a)

5.(b) 6.(a) 7.(c) 8.(d) 5. (d) 6. (b) 7. (b) 8. (c)
9.(c) 10.(d) 11.(c) 12.(a) 9. (c) 10. (a,c,d) 11. (b,c,d) 12. (a,c)
13.(a) 14.(d) 15.(a) 16.(d)
13. (9.00) 14. (6.00) 15. (b) 16. (d)
17.(d) 18.(a) 19.(c) 20.(c)
17. (c) 18. (c) 19. (b) 20. (b)
21.(c) 22.(a) 23.(c) 24.(c)
21. (a) 22. (d)
25.(b) 26.(b) 27.(d) 28.(b)
29.(c) 30.(d) 31.(a,d) 32.(a,b)
33.(a,b) 34.(b,d) 35.(b,c) 36.(a,d)
37.(a,c) 38.(a,b,c) 39.(b) 40.(a)
41.(c) 42.(a) 43.(d) 44.(a)
45.(a) 46.(b) 47.(c)
48.(A–P, R, S; B–P, Q, R, S; C–P, Q, R, S; D–P, R, S)
49.(d) 50. (c) 51. (a,b) 52. (c)
53. (d) 54. (a) 55. (b) 56. (c)
MASTER INDEX
VOLUME 1:
Solutions
Solid State
General Organic Chemistry (Revision) & Isomerism
Alkyl and Aryl Halides
Alcohols, Phenols and Ethers

VOLUME 2:
Aldehydes and Ketones
Biomolecules
Carboxylic Acid and Its Derivatives
Amines
Polymers

VOLUME 3:
p -Block Elements (group 15-18)
Metallurgy
d and f Block Elements
Chemistry in Everyday Life
Practical Organic Chemistry
Qualitative Analysis

VOLUME 4:
Coordination Compounds
Chemical Kinetics
Electrochemistry
Surface Chemistry
 Creating Impact at Scale

65 Million+
Monthly
Youtube Views

49 Million+ 40+ Countries

Monthly Where Students
Web + App Visitors Take Live Classes

25 Million+ 26 Million+
Monthly Active Hours of
Users Live Learning

25 43
Parents
Happy
Trust
Students
Vedantu
MILLION+ MILLION+
 Our Results Speak for Us

JEE Main 2023

170
Vedantu Students
JEE Scored Above 99%ile

1000+ Vedantu Students Scored

Above 90%ile

JEE Advanced 2022 JEE Advanced 2021

2700+ Vedantu Students Cleared JEE Main in 2022

1500+ Vedantu Students Cleared JEE Adv. 2022 1500+ Vedantu Students Cleared JEE Adv. 2021

NEET (UG) 2022 NEET (UG) 2021

1000+ Vedantu Students Qualified NEET 2022 1172+ Vedantu Students Qualified NEET 2021

CBSE Class 12 ISC Class 12 CBSE Class 10

Annmary
Aatman Upreti Shreya Roshan Aastha N Raj Gitanjali Rajulal Shreya Nigam Khushi Arora Anshika Singha
Santhosh
98.4% 98.4% 98.0% 99.8% 98.4% 99.8% 99.6% 99.4%

ICSE Class 10

M.D.Sriya Varshil J Patel Mohammad Y Devika Sajeev Sakshi Semwal Aloki Upadhyay Ishita Surana Saumya Gupta

99.4% 97.4% 97.2% 97.2% 97.2% 99.4% 99.2% 99.2%

#HereForRealAchievers