Unit 1

Some Basic Concepts of Chemistry

Chemistry is the science of molecules and their

transformations. It is the science not so much of the one
hundred elements but of the infinite variety of molecules
After studying this unit, you will be that may be built from them.
able to
• appreciate the contribution of India Roald Hoffmann
in the development of chemistry
understand the role of chemistry
in different spheres of life; Science can be viewed as a continuing human effort to
• explain the characteristics of three systematise knowledge for describing and understanding
states of matter; nature. You have learnt in your previous classes that we
• classify different substances come across diverse substances present in nature and
into elements, compounds and changes in them in daily life. Curd formation from milk,
mixtures;
formation of vinegar from sugarcane juice on keeping
• use scientific notations and for prolonged time and rusting of iron are some of the
determine significant figures;
examples of changes which we come across many times.
• differentiate between precision and
For the sake of convenience, science is sub-divided into
accuracy;
various disciplines: chemistry, physics, biology, geology,
• define SI base units and convert
etc. The branch of science that studies the preparation,
physical quantities from one
system of units to another; properties, structure and reactions of material substances
• explain various laws of chemical
is called chemistry.
combination; Development of chemistry
• appreciate significance of atomic Chemistry, as we understand it today, is not a very old
mass, average atomic mass,
discipline. Chemistry was not studied for its own sake, rather
molecular mass and formula mass;
it came up as a result of search for two interesting things:
• describe the terms – mole and
molar mass;
i. Philosopher’s stone (Paras) which would convert
all baser metals e.g., iron and copper into gold.
• calculate the mass per cent of
component elements constituting
ii. ‘Elexir of life’ which would grant immortality.
a compound; People in ancient India, already had the knowledge of
• determine empirical formula and many scientific phenomenon much before the advent of
molecular formula for a compound modern science. They applied that knowledge in various
from the given experimental data; walks of life. Chemistry developed mainly in the form
and of Alchemy and Iatrochemistry during 1300-1600 CE.
• perform the stoichiometric Modern chemistry took shape in the 18th century Europe,
calculations. after a few centuries of alchemical traditions which were
introduced in Europe by the Arabs.

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 2 chemistry

Other cultures – especially the Chinese be shown to agree with modern scientific
and the Indian – had their own alchemical findings. Copper utensils, iron, gold, silver
traditions. These included much knowledge of ornaments and terracotta discs and painted
chemical processes and techniques. grey pottery have been found in many
In ancient India, chemistry was called archaeological sites in north India. Sushruta
Rasayan Shastra, Rastantra, Ras Kriya or Samhita explains the importance of Alkalies.
Rasvidya. It included metallurgy, medicine, The Charaka Samhita mentions ancient
manufacture of cosmetics, glass, dyes, etc. indians who knew how to prepare sulphuric
Systematic excavations at Mohenjodaro in acid, nitric acid and oxides of copper, tin and
Sindh and Harappa in Punjab prove that the zinc; the sulphates of copper, zinc and iron
story of development of chemistry in India
and the carbonates of lead and iron.
is very old. Archaeological findings show
that baked bricks were used in construction Rasopanishada describes the preparation
work. It shows the mass production of of gunpowder mixture. Tamil texts also
pottery, which can be regarded as the earliest describe the preparation of fireworks using
chemical process, in which materials were sulphur, charcoal, saltpetre (i.e., potassium
mixed, moulded and subjected to heat by nitrate), mercury, camphor, etc.
using fire to achieve desirable qualities. Nagarjuna was a great Indian scientist. He
Remains of glazed pottery have been found in was a reputed chemist, an alchemist and a
Mohenjodaro. Gypsum cement has been used metallurgist. His work Rasratnakar deals with
in the construction work. It contains lime, the formulation of mercury compounds. He
sand and traces of CaCO3. Harappans made has also discussed methods for the extraction
faience, a sort of glass which was used in of metals, like gold, silver, tin and copper. A
ornaments. They melted and forged a variety book, Rsarnavam, appeared around 800 CE.
of objects from metals, such as lead, silver,
It discusses the uses of various furnaces,
gold and copper. They improved the hardness
ovens and crucibles for different purposes. It
of copper for making artefacts by using tin
describes methods by which metals could be
and arsenic. A number of glass objects were
found in Maski in South India (1000–900 identified by flame colour.
BCE), and Hastinapur and Taxila in North Chakrapani discovered mercury sulphide.
India (1000–200 BCE). Glass and glazes were The credit for inventing soap also goes to him.
coloured by addition of colouring agents like He used mustard oil and some alkalies as
metal oxides. ingredients for making soap. Indians began
Copper metallurgy in India dates back to making soaps in the 18th century CE. Oil of
the beginning of chalcolithic cultures in the Eranda and seeds of Mahua plant and calcium
subcontinent. There are much archeological carbonate were used for making soap.
evidences to support the view that technologies The paintings found on the walls of Ajanta
for extraction of copper and iron were and Ellora, which look fresh even after ages,
developed indigenously. testify to a high level of science achieved in
According to Rigveda, tanning of leather ancient India. Varähmihir’s Brihat Samhita is
and dying of cotton were practised during a sort of encyclopaedia, which was composed
1000–400 BCE. The golden gloss of the in the sixth century CE. It informs about the
black polished ware of northen India could preparation of glutinous material to be applied
not be replicated and is still a chemical on walls and roofs of houses and temples. It
mystery. These wares indicate the mastery was prepared entirely from extracts of various
with which kiln temperatures could be plants, fruits, seeds and barks, which were
controlled. Kautilya’s Arthashastra describes concentrated by boiling, and then, treated
the production of salt from sea. with various resins. It will be interesting to
A vast number of statements and material test such materials scientifically and assess
described in the ancient Vedic literature can them for use.

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 Some Basic Concepts of Chemistry 3

A number of classical texts, like forces cause interaction between them. He

Atharvaveda (1000 BCE) mention some conceptualised this theory around 2500 years
dye stuff, the material used were turmeric, before John Dalton (1766-1844).
madder, sunflower, orpiment, cochineal and Charaka Samhita is the oldest Ayurvedic
lac. Some other substances having tinting epic of India. It describes the treatment of
property were kamplcica, pattanga and jatuka. diseases. The concept of reduction of particle
Varähmihir’s Brihat Samhita gives size of metals is clearly discussed in Charaka
references to perfumes and cosmetics. Samhita. Extreme reduction of particle size is
Recipes for hair dying were made from plants, termed as nanotechnology. Charaka Samhita
like indigo and minerals like iron power, describes the use of bhasma of metals in the
black iron or steel and acidic extracts of sour treatment of ailments. Now-a-days, it has
rice gruel. Gandhayukli describes recipes been proved that bhasmas have nanoparticles
for making scents, mouth perfumes, bath of metals.
powders, incense and talcum power. After the decline of alchemy, Iatrochemistry
Paper was known to India in the 17th reached a steady state, but it too declined due
century as account of Chinese traveller I-tsing to the introduction and practise of western
describes. Excavations at Taxila indicate that medicinal system in the 20th century. During
ink was used in India from the fourth century. this period of stagnation, pharmaceutical
Colours of ink were made from chalk, red lead industry based on Ayurveda continued to
and minimum. exist, but it too declined gradually. It took
It seems that the process of fermentation about 100-150 years for Indians to learn
was well-known to Indians. Vedas and and adopt new techniques. During this time,
Kautilya’s Arthashastra mention about foreign products poured in. As a result,
many types of liquors. Charaka Samhita also indigenous traditional techniques gradually
mentions ingredients, such as barks of plants, declined. Modern science appeared in Indian
stem, flowers, leaves, woods, cereals, fruits scene in the later part of the nineteenth
and sugarcane for making Asavas. century. By the mid-nineteenth century,
European scientists started coming to India
The concept that matter is ultimately
and modern chemistry started growing.
made of indivisible building blocks, appeared
in India a few centuries BCE as a part of From the above discussion, you have learnt
philosophical speculations. Acharya Kanda, that chemistry deals with the composition,
born in 600 BCE, originally known by the structure, properties and interection of matter
name Kashyap, was the first proponent and is of much use to human beings in daily
of the ‘atomic theory’. He formulated the life. These aspects can be best described and
theory of very small indivisible particles, understood in terms of basic constituents of
which he named ‘Paramãnu’ (comparable matter that are atoms and molecules. That
to atoms). He authored the text Vaiseshika is why, chemistry is also called the science of
Sutras. According to him, all substances are atoms and molecules. Can we see, weigh and
aggregated form of smaller units called atoms perceive these entities (atoms and molecules)?
(Paramãnu), which are eternal, indestructible, Is it possible to count the number of atoms
spherical, suprasensible and in motion in and molecules in a given mass of matter and
the original state. He explained that this have a quantitative relationship between the
individual entity cannot be sensed through mass and the number of these particles?
any human organ. Kanda added that there We will get the answer of some of these
are varieties of atoms that are as different as questions in this Unit. We will further describe
the different classes of substances. He said how physical properties of matter can be
these (Paramãnu) could form pairs or triplets, quantitatively described using numerical
among other combinations and unseen values with suitable units.

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 4 chemistry

1.1 IMPORTANCE OF CHEMISTRY many big environmental problems continue to

Chemistry plays a central role in science and be matters of grave concern to the chemists.
is often intertwined with other branches of One such problem is the management of the
science. Green House gases, like methane, carbon
dioxide, etc. Understanding of biochemical
Principles of chemistry are applicable processes, use of enzymes for large-scale
in diverse areas, such as weather patterns, production of chemicals and synthesis of new
functioning of brain and operation of a exotic material are some of the intellectual
computer, production in chemical industries, challenges for the future generation of
manufacturing fertilisers, alkalis, acids, salts, chemists. A developing country, like India,
dyes, polymers, drugs, soaps, detergents, needs talented and creative chemists for
metals, alloys, etc., including new material. accepting such challenges. To be a good
Chemistry contributes in a big way to the chemist and to accept such challanges, one
national economy. It also plays an important needs to understand the basic concepts of
role in meeting human needs for food, chemistry, which begin with the concept of
healthcare products and other material matter. Let us start with the nature of matter.
aimed at improving the quality of life. This 1.2 Nature of Matter
is exemplified by the large-scale production You are already familiar with the term matter
of a variety of fertilisers, improved variety from your earlier classes. Anything which has
of pesticides and insecticides. Chemistry mass and occupies space is called matter.
provides methods for the isolation of life- Everything around us, for example, book, pen,
saving drugs from natural sources and pencil, water, air, all living beings, etc., are
makes possible synthesis of such drugs. composed of matter. You know that they have
Some of these drugs are cisplatin and mass and they occupy space. Let us recall the
taxol, which are effective in cancer therapy. characteristics of the states of matter, which
The drug AZT (Azidothymidine) is used for you learnt in your previous classes.
helping AIDS patients.
Chemistry contributes to a large extent in 1.2.1 States of Matter
the development and growth of a nation. With You are aware that matter can exist in three
a better understanding of chemical principles physical states viz. solid, liquid and gas.
it has now become possible to design and The constituent particles of matter in these
synthesise new material having specific three states can be represented as shown in
magnetic, electric and optical properties. This Fig. 1.1.
has lead to the production of superconducting Particles are held very close to each other
ceramics, conducting polymers, optical fibres, in solids in an orderly fashion and there is not
etc. Chemistry has helped in establishing much freedom of movement. In liquids, the
industries which manufacture utility goods, particles are close to each other but they can
like acids, alkalies, dyes, polymesr metals, move around. However, in gases, the particles
etc. These industries contribute in a big way are far apart as compared to those present in
to the economy of a nation and generate solid or liquid states and their movement is
employment. easy and fast. Because of such arrangement
In recent years, chemistry has helped in of particles, different states of matter exhibit
dealing with some of the pressing aspects the following characteristics:
of environmental degradation with a fair (i) Solids have definite volume and definite
degree of success. Safer alternatives to shape.
environmentally hazardous refrigerants, (ii) Liquids have definite volume but do
like CFCs (chlorofluorocarbons), responsible not have definite shape. They take the
for ozone depletion in the stratosphere, have shape of the container in which they are
been successfully synthesised. However, placed.

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 Some Basic Concepts of Chemistry 5

Fig. 1.1 Arrangement of particles in solid, liquid Fig. 1.2 Classification of matter
and gaseous state

(iii) Gases have neither definite volume nor completely mix with each other. This means
definite shape. They completely occupy particles of components of the mixture are
the space in the container in which they uniformly distributed throughout the bulk of
are placed. the mixture and its composition is uniform
throughout. Sugar solution and air are the
These three states of matter are
examples of homogeneous mixtures. In
interconvertible by changing the conditions
contrast to this, in a heterogeneous mixture,
of temperature and pressure.
the composition is not uniform throughout
Solid liquid Gas and sometimes different components are
On heating, a solid usually changes to visible. For example, mixtures of salt and
a liquid, and the liquid on further heating sugar, grains and pulses along with some
changes to gas (or vapour). In the reverse dirt (often stone pieces), are heterogeneous
process, a gas on cooling liquifies to the liquid mixtures. You can think of many more
and the liquid on further cooling freezes to examples of mixtures which you come across
the solid. in the daily life. It is worthwhile to mention
here that the components of a mixture can
1.2.2. Classification of Matter be separated by using physical methods,
In Class IX (Chapter 2), you have learnt that such as simple hand-picking, filtration,
at the macroscopic or bulk level, matter can crystallisation, distillation, etc.
be classified as mixture or pure substance.
Pure substances have characteristics
These can be further sub-divided as shown
different from mixtures. Constituent particles
in Fig. 1.2.
of pure substances have fixed composition.
When all constituent particles of a Copper, silver, gold, water and glucose are
substance are same in chemical nature, it some examples of pure substances. Glucose
is said to be a pure substance. A mixture contains carbon, hydrogen and oxygen in
contains many types of particles. a fixed ratio and its particles are of same
A mixture contains particles of two or composition. Hence, like all other pure
more pure substances which may be present substances, glucose has a fixed composition.
in it in any ratio. Hence, their composition is Also, its constituents—carbon, hydrogen
variable. Pure substances forming mixture and oxygen—cannot be separated by simple
are called its components. Many of the physical methods.
substances present around you are mixtures. Pure substances can further be classified
For example, sugar solution in water, air, into elements and compounds. Particles
tea, etc., are all mixtures. A mixture may of an element consist of only one type of
be homogeneous or heterogeneous. In a atoms. These particles may exist as atoms or
homogeneous mixture, the components molecules. You may be familiar with atoms

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 6 chemistry

and molecules from the previous classes;

however, you will be studying about them
in detail in Unit 2. Sodium, copper, silver,
hydrogen, oxygen, etc., are some examples
of elements. Their all atoms are of one type.
However, the atoms of different elements Water molecule Carbon dioxide
are different in nature. Some elements, (H2O) molecule (CO2)
such as sodium or copper, contain atoms Fig. 1.4 A depiction of molecules of water and
as their constituent particles, whereas, in carbon dioxide
some others, the constituent particles are
molecules which are formed by two or more elements are present in a compound in a fixed
atoms. For example, hydrogen, nitrogen and and definite ratio and this ratio is characteristic
oxygen gases consist of molecules, in which of a particular compound. Also, the properties
two atoms combine to give their respective of a compound are different from those of its
molecules. This is illustrated in Fig. 1.3. constituent elements. For example, hydrogen
and oxygen are gases, whereas, the compound
formed by their combination i.e., water is a
liquid. It is interesting to note that hydrogen
burns with a pop sound and oxygen is a
supporter of combustion, but water is used
as a fire extinguisher.
1.3 Properties of Matter and
their Measurement

1.3.1 Physical and chemical properties

Every substance has unique or characteristic
properties. These properties can be classified
into two categories — physical properties,
such as colour, odour, melting point, boiling
point, density, etc., and chemical properties,
like composition, combustibility, ractivity with
Fig. 1.3 A representation of atoms and molecules
acids and bases, etc.
When two or more atoms of different Physical properties can be measured
elements combine together in a definite ratio, or observed without changing the identity
the molecule of a compound is obtained. or the composition of the substance. The
Moreover, the constituents of a compound measurement or observation of chemical
cannot be separated into simpler substances properties requires a chemical change to
by physical methods. They can be separated occur. Measurement of physical properties
by chemical methods. Examples of some does not require occurance of a chemical
change. The examples of chemical properties
compounds are water, ammonia, carbon
are characteristic reactions of different
dioxide, sugar, etc. The molecules of water
substances; these include acidity or basicity,
and carbon dioxide are represented in Fig. 1.4.
combustibility, etc. Chemists describe,
Note that a water molecule comprises interpret and predict the behaviour of
two hydrogen atoms and one oxygen atom. substances on the basis of knowledge of their
Similarly, a molecule of carbon dioxide physical and chemical properties, which are
contains two oxygen atoms combined with determined by careful measurement and
one carbon atom. Thus, the atoms of different experimentation. In the following section, we

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 Some Basic Concepts of Chemistry 7

will learn about the measurement of physical

properties. Maintaining the National
Standards of Measurement
1.3.2 Measurement of physical properties
The system of units, including unit
Quantitative measurement of properties is definitions, keeps on changing with time.
reaquired for scientific investigation. Many Whenever the accuracy of measurement of a
properties of matter, such as length, area, particular unit was enhanced substantially
volume, etc., are quantitative in nature. Any by adopting new principles, member nations
quantitative observation or measurement is of metre treaty (signed in 1875), agreed
represented by a number followed by units to change the formal definition of that
in which it is measured. For example, length unit. Each modern industrialised country,
of a room can be represented as 6 m; here, including India, has a National Metrology
Institute (NMI), which maintains standards of
6 is the number and m denotes metre, the
measurements. This responsibility has been
unit in which the length is measured. given to the National Physical Laboratory
Earlier, two different systems of (NPL), New Delhi. This laboratory establishes
measurement, i.e., the English System experiments to realise the base units and
and the Metric System were being used derived units of measurement and maintains
National Standards of Measurement. These
in different parts of the world. The metric
standards are periodically inter-compared
system, which originated in France in late with standards maintained at other National
eighteenth century, was more convenient as Metrology Institutes in the world, as well
it was based on the decimal system. Late, as those, established at the International
need of a common standard system was felt Bureau of Standards in Paris.
by the scientific community. Such a system
was established in 1960 and is discussed in governmental treaty organisation created by a
detail below. diplomatic treaty known as Metre Convention,
1.3.3 The International System of Units (SI) which was signed in Paris in 1875.
The International System of Units (in The SI system has seven base units
French Le Systeme International d’Unités and they are listed in Table 1.1. These units
— abbreviated as SI) was established by pertain to the seven fundamental scientific
the 11th General Conference on Weights and quantities. The other physical quantities,
Measures (CGPM from Conference Generale such as speed, volume, density, etc., can be
des Poids et Measures). The CGPM is an inter- derived from these quantities.

Table 1.1 Base Physical Quantities and their Units

Base Physical Symbol for Name of Symbol for
Quantity Quantity SI Unit SI Unit
Length l metre m
Mass m kilogram kg
Time t second s
Electric current I ampere A
Thermodynamic T kelvin K
temperature
Amount of n mole mol
substance candela
Iv cd
Luminous
intensity

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 8 chemistry

The definitions of the SI base units are These prefixes are listed in Table 1.3.
given in Table 1.2. Let us now quickly go through some of
The SI system allows the use of prefixes to the quantities which you will be often using
indicate the multiples or submultiples of a unit. in this book.

Table 1.2 Definitions of SI Base Units

The metre, symbol m is the SI unit of length. It is defined by

taking the fixed numerical value of the speed of light in vacuum
Unit of length metre
c to be 299792458 when expressed in the unit ms–1, where
the second is defined in terms of the caesium frequencyV Cs.

The kilogram, symbol kg. is the SI unit of mass. It is defined

by taking the fixed numerical value of the planck constant h to
Unit of mass kilogram be 6.62607015×10–34 when expressed in the unit Js, which is
equal to kgm2s–1, where the metre and the second are defined
in terms of c and V Cs.

The second symbol s, is the SI unit of time. It is defined by

taking the fixed numerical value of the caesium frequency V Cs,
Unit of time second the unperturbed ground-state hyperfine transition frequency
of the caesium-133 atom, to be 9192631770 when expressed
in the unit Hz, which is equal to s–1.

The ampere, symbol A, is the SI unit of electric current. It is

defined by taking the fixed numerical value of the elementary
Unit of electric
ampere charge e to be 1.602176634×10–19 when expressed in the unit
current
C, which is equal to As, where the second is defined in terms
of V Cs.

The kelvin, symbol k, is the SI unit of thermodynamic

temperature. It is defined by taking the fixed numerical value
Unit of
of the Boltzmann constant k to be 1.380649×10–23 when
thermodynamic kelvin
expressed in the unit JK–1, which is equal to kgm2s–2k–1 where
temperature
the kilogram, metre and second are defined in terms of h, c
and V Cs.

The mole, symbol mol, is the SI unit of amount of substance.

One mole contains exactly 6.02214076×10 23 elementary
entities. This number is the fixed numerical value of the
Avogadro constant, NA, when expressed in the unit mol–1 and
Unit of amount
mole is called the Avogadro number. The amount of substance,
of substance
symbol n, of a system is a measure of the number of specified
elementary entities. An elementary entity may be an atom, a
molecule, an ion, an electron, any other particle or specified
group of particles.

The candela, symbol cd is the SI unit of luminous intensity in

a given direction. It is defined by taking the fixed numerical
value of the luminous efficacy of monochromatic radiation
Unit of luminous
Candela of frequency 540×1012 Hz, Kcd, to be 683 when expressed
Intensity
in the unit lm·W–1, which is equal to cd·sr·W–1, or cd sr kg–1
m–2s3, where the kilogram, metre and second are defined in
terms of h, c and V Cs.

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 Some Basic Concepts of Chemistry 9

Table 1.3 Prefixes used in the SI System

Multiple Prefix Symbol

10–24 yocto y
10–21 zepto z
10 –18
atto a
10–15 femto f
10 –12
pico p
10 –9
nano n
10–6 micro µ
10 –3
milli m
10–2 centi c
10 –1
deci d
10 deca da
102 hecto h
10 3
kilo k
106 mega M Fig. 1.5 Analytical balance
10 9
giga G
10 12
tera T
SI system, volume has units of m3. But again,
1015 peta P in chemistry laboratories, smaller volumes
1018 exa E are used. Hence, volume is often denoted in
1021 zeta Z cm3 or dm3 units.
10 24
yotta Y A common unit, litre (L) which is not an
SI unit, is used for measurement of volume
1.3.4 Mass and Weight
of liquids.
Mass of a substance is the amount of matter
1 L = 1000 mL, 1000 cm3 = 1 dm3
present in it, while weight is the force
Fig. 1.6 helps to visualise these relations.
exerted by gravity on an object. The mass of
a substance is constant, whereas, its weight
may vary from one place to another due to
change in gravity. You should be careful in
using these terms.
The mass of a substance can be determined
accurately in the laboratory by using an
analytical balance (Fig. 1.5).
The SI unit of mass as given in Table 1.1 is
kilogram. However, its fraction named as gram
(1 kg = 1000 g), is used in laboratories due
to the smaller amounts of chemicals used in
chemical reactions.
1.3.5 Volume
Volume is the amont of space occupied by a Fig. 1.6 Different units used to express
substance. It has the units of (length)3. So in volume

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 10 chemistry

In the laboratory, the volume of liquids fahrenheit) and K (kelvin). Here, K is the
or solutions can be measured by graduated SI unit. The thermometers based on these
cylinder, burette, pipette, etc. A volumetric scales are shown in Fig. 1.8. Generally,
flask is used to prepare a known volume of a the thermometer with celsius scale are
solution. These measuring devices are shown calibrated from 0° to 100°, where these two
in Fig. 1.7. temperatures are the freezing point and
the boiling point of water, respectively. The
fahrenheit scale is represented between 32°
to 212°.
The temperatures on two scales are
related to each other by the following
relationship:
9
F  C  32
5
The kelvin scale is related to celsius scale
as follows:
K = °C + 273.15
It is interesting to note that temperature
below 0 °C (i.e., negative values) are possible
in Celsius scale but in Kelvin scale, negative
Fig. 1.7 Some volume measuring devices
temperature is not possible.
1.3.6 Density
The two properties — mass and volume
discussed above are related as follows:
Mass
Density =
Volume
Density of a substance is its amount of mass
per unit volume. So, SI units of density can
be obtained as follows:

SI unit of density =

kg
= 3
or kg m–3
m
This unit is quite large and a chemist often
expresses density in g cm–3, where mass is
expressed in gram and volume is expressed
in cm3. Density of a substance tells us about Fig. 1.8 Thermometers using different
temperature scales
how closely its particles are packed. If density
is more, it means particles are more closely
1.4 Uncertainty in Measurement
packed.
Many a time in the study of chemistry, one
1.3.7 Temperature has to deal with experimental data as well as
There are three common scales to measure theoretical calculations. There are meaningful
temperature — °C (degree celsius), °F (degree ways to handle the numbers conveniently and

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 Some Basic Concepts of Chemistry 11

present the data realistically with certainty to

Reference Standard the extent possible. These ideas are discussed
below in detail.
After defining a unit of measurement such as
the kilogram or the metre, scientists agreed 1.4.1 Scientific Notation
on reference standards that make it possible
As chemistry is the study of atoms and
to calibrate all measuring devices. For getting
molecules, which have extremely low masses
reliable measurements, all devices such as
metre sticks and analytical balances have
and are present in extremely large numbers,
been calibrated by their manufacturers a chemist has to deal with numbers as large
to give correct readings. However, each of as 602, 200,000,000,000,000,000,000 for the
these devices is standardised or calibrated molecules of 2 g of hydrogen gas or as small as
against some reference. The mass standard 0.00000000000000000000000166 g mass of
is the kilogram since 1889. It has been a H atom. Similarly, other constants such as
defined as the mass of platinum-iridium Planck’s constant, speed of light, charges on
(Pt-Ir) cylinder that is stored in an airtight particles, etc., involve numbers of the above
jar at International Bureau of Weights magnitude.
and Measures in Sevres, France. Pt-Ir was
chosen for this standard because it is highly It may look funny for a moment to
resistant to chemical attack and its mass write or count numbers involving so many
will not change for an extremely long time. zeros but it offers a real challenge to do
Scientists are in search of a new simple mathematical operations of addition,
standard for mass. This is being attempted subtraction, multiplication or division with
through accurate determination of Avogadro such numbers. You can write any two
constant. Work on this new standard focuses
numbers of the above type and try any one
on ways to measure accurately the number
of the operations you like to accept as a
of atoms in a well-defined mass of sample.
One such method, which uses X-rays to
challenge, and then, you will really appreciate
determine the atomic density of a crystal of the difficulty in handling such numbers.
ultrapure silicon, has an accuracy of about This problem is solved by using scientific
1 part in 106 but has not yet been adopted to notation for such numbers, i.e., exponential
serve as a standard. There are other methods notation in which any number can be
but none of them are presently adequate to represented in the form N × 10n, where n is an
replace the Pt-Ir cylinder. No doubt, changes
exponent having positive or negative values
are expected within this decade.
and N is a number (called digit term) which
The metre was originally defined as the
varies between 1.000... and 9.999....
length between two marks on a Pt-Ir bar
kept at a temperature of 0°C (273.15 K). In Thus, we can write 232.508 as
1960 the length of the metre was defined as 2.32508 × 102 in scientific notation. Note that
1.65076373 × 106 times the wavelength of while writing it, the decimal had to be moved
light emitted by a krypton laser. Although to the left by two places and same is the
this was a cumbersome number, it preserved exponent (2) of 10 in the scientific notation.
the length of the metre at its agreed value.
The metre was redefined in 1983 by CGPM
Similarly, 0.00016 can be written as
as the length of path travelled by light in 1.6 × 10 –4 . Here, the decimal has to be
vacuum during a time interval of 1/299 792 moved four places to the right and (–4) is the
458 of a second. Similar to the length and exponent in the scientific notation.
the mass, there are reference standards for While performing mathematical operations
other physical quantities. on numbers expressed in scientific notations,
the following points are to be kept in mind.

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 12 chemistry

Multiplication and Division mass obtained by an analytical balance is

These two operations follow the same rules slightly higher than the mass obtained by
which are there for exponential numbers, i.e. using a platform balance. Therefore, digit 4
placed after decimal in the measurement by
platform balance is uncertain.
5.6  10   6.9  10  = 5.6  6.9 10 
5 8 58

The uncertainty in the experimental

= 5.6  6.9  1013
or the calculated values is indicated by
= 38..64  1013 mentioning the number of significant
= 3.864  1014 figures. Significant figures are meaningful
digits which are known with certainty plus
9.8  10   2.5  10  = 9.8  2.5 10   
2 6 2  6
one which is estimated or uncertain. The
= 9.8  2.5 10  2  6 uncertainty is indicated by writing the certain
digits and the last uncertain digit. Thus, if we
= 24.50  10 8 write a result as 11.2 mL, we say the 11 is
= 2.450  10 7 certain and 2 is uncertain and the uncertainty
would be +1 in the last digit. Unless otherwise
2.7  10 3
5  104
5.5
 
= 2.7  5.5 10 3  4 = 0.4909  10 7 stated, an uncertainty of +1 in the last digit
is always understood.
= 4.909  10 8 There are certain rules for determining
the number of significant figures. These are
Addition and Subtraction stated below:
For these two operations, first the numbers are (1) All non-zero digits are significant. For
written in such a way that they have the same example in 285 cm, there are three
exponent. After that, the coefficients (digit significant figures and in 0.25 mL, there
terms) are added or subtracted as the case are two significant figures.
may be. (2) Zeros preceding to first non-zero digit
Thus, for adding 6.65×104 and 8.95×103, are not significant. Such zero indicates
exponent is made same for both the numbers. the position of decimal point. Thus,
Thus, we get (6.65×104) + (0.895×104) 0.03 has one significant figure and
Then, these numbers can be added as follows 0.0052 has two significant figures.
(6.65 + 0.895)×104 = 7.545×104 (3) Zeros between two non-zero digits
Similarly, the subtraction of two numbers can are significant. Thus, 2.005 has four
be done as shown below: significant figures.
(2.5 × 10–2) – (4.8 ×10–3) (4) Zeros at the end or right of a number
are significant, provided they are on
= (2.5 × 10–2) – (0.48 × 10–2) the right side of the decimal point. For
= (2.5 – 0.48)×10–2 = 2.02 × 10–2 example, 0.200 g has three significant
figures. But, if otherwise, the terminal
1.4.2 Significant Figures zeros are not significant if there is no
Every experimental measurement has decimal point. For example, 100 has
some amount of uncertainty associated only one significant figure, but 100 has
with it because of limitation of measuring three significant figures and 100.0 has
instrument and the skill of the person making four significant figures. Such numbers
the measurement. For example, mass of an are better represented in scientific
object is obtained using a platform balance notation. We can express the number
and it comes out to be 9.4g. On measuring 100 as 1×102 for one significant figure,
the mass of this object on an analytical 1.0×102 for two significant figures and
balance, the mass obtained is 9.4213g. The 1.00×102 for three significant figures.

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 Some Basic Concepts of Chemistry 13

(5) Counting the numbers of object, for Here, 18.0 has only one digit after the decimal
example, 2 balls or 20 eggs, have infinite point and the result should be reported only
significant figures as these are exact up to one digit after the decimal point, which
numbers and can be represented by is 31.1.
writing infinite number of zeros after
placing a decimal i.e., 2 = 2.000000 or Multiplication and Division of
20 = 20.000000. Significant Figures
In numbers written in scientific notation, In these operations, the result must be
all digits are significant e.g., 4.01×102 has reported with no more significant figures as
three significant figures, and 8.256×10–3 has in the measurement with the few significant
four significant figures. figures.
However, one would always like the results
to be precise and accurate. Precision and 2.5×1.25 = 3.125
accuracy are often referred to while we talk Since 2.5 has two significant figures,
about the measurement. the result should not have more than two
Precision refers to the closeness of significant figures, thus, it is 3.1.
various measurements for the same quantity. While limiting the result to the required
However, accuracy is the agreement of a number of significant figures as done in the
particular value to the true value of the above mathematical operation, one has to
result. For example, if the true value for a keep in mind the following points for rounding
result is 2.00 g and student ‘A’ takes two off the numbers
measurements and reports the results as 1.95 1. If the rightmost digit to be removed is
g and 1.93 g. These values are precise as they more than 5, the preceding number is
are close to each other but are not accurate. increased by one. For example, 1.386. If
Another student ‘B’ repeats the experiment we have to remove 6, we have to round
and obtains 1.94 g and 2.05 g as the results it to 1.39.
for two measurements. These observations 2. If the rightmost digit to be removed is
are neither precise nor accurate. When the less than 5, the preceding number is not
third student ‘C’ repeats these measurements changed. For example, 4.334 if 4 is to
and reports 2.01 g and 1.99 g as the result, be removed, then the result is rounded
these values are both precise and accurate. upto 4.33.
This can be more clearly understood from the 3. If the rightmost digit to be removed is 5,
data given in Table 1.4. then the preceding number is not changed
Table 1.4 Data to Illustrate Precision if it is an even number but it is increased
and Accuracy by one if it is an odd number. For example,
Measurements/g if 6.35 is to be rounded by removing 5, we
1 2 Average (g) have to increase 3 to 4 giving 6.4 as the
result. However, if 6.25 is to be rounded
Student A 1.95 1.93 1.940
off it is rounded off to 6.2.
Student B 1.94 2.05 1.995
1.4.3 Dimensional Analysis
Student C 2.01 1.99 2.000
Often while calculating, there is a need to
Addition and Subtraction of convert units from one system to the other.
Significant Figures The method used to accomplish this is called
The result cannot have more digits to the right factor label method or unit factor method
of the decimal point than either of the original or dimensional analysis. This is illustrated
numbers. 12.11 below.
18.0 Example
1.012 A piece of metal is 3 inch (represented by in)
31.122 long. What is its length in cm?

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 14 chemistry

Solution The above is multiplied by the unit factor

We know that 1 in = 2.54 cm 1 m3 2 m3
2  1000 cm 3  6   2  10 3 m 3
From this equivalence, we can write 10 cm 3 103

1 in 2.54 cm Example
= 1=
2.54 cm 1 in How many seconds are there in 2 days?
Solution
1 in 2.54 cm Here, we know 1 day = 24 hours (h)
Thus, equals 1 and
2.54 cm 1 in 1 day 24 h
or = 1=
24 h 1 day
also equals 1. Both of these are called unit then, 1h = 60 min
factors. If some number is multiplied by these 1h 60 min
unit factors (i.e., 1), it will not be affected or = 1=
60 min 1h
otherwise.
so, for converting 2 days to seconds,
Say, the 3 in given above is multiplied by
the unit factor. So, i.e., 2 days – – – – – – = – – – seconds
2.54 cm The unit factors can be multiplied in
3 in = 3 in × = 3 × 2.54 cm = 7.62 cm
1 in series in one step only as follows:
24 h 60 min 60 s
Now, the unit factor by which multiplication 2 day × × ×
2.54 cm 1 day 1h 1 min
is to be done is that unit factor ( in
1 in = 2 × 24 × 60 × 60 s
= 172800 s
the above case) which gives the desired units
i.e., the numerator should have that part 1.5 Laws of Chemical
which is required in the desired result. Combinations
It should also be noted in the above The combination of elements
example that units can be handled just like to form compounds is
other numerical part. It can be cancelled, governed by the following five
divided, multiplied, squared, etc. Let us study basic laws.
Antoine Lavoisier
one more example. (1743–1794)
1.5.1 Law of Conservation
Example of Mass
A jug contains 2 L of milk. Calculate the This law was put forth by Antoine Lavoisier
volume of the milk in m3. in 1789. He performed careful experimental
Solution studies for combustion reactions and reached
Since 1 L = 1000 cm3 to the conclusion that in all physical and
and 1m = 100 cm, which gives chemical changes, there is no net change in
1m 100 cm mass duting the process. Hence, he reached
= 1= to the conclusion that matter can neither be
100 cm 1m
created nor destroyed. This is called ‘Law
To get m3 from the above unit factors, the of Conservation of Mass’. This law formed
first unit factor is taken and it is cubed. the basis for several later developments in
 1m 
3 chemistry. Infact, this was the result of exact
1 m3
 1  1
3
 100 cm   6 3 measurement of masses of reactants and
10 cm
products, and carefully planned experiments
Now 2 L = 2 ×1000 cm3 performed by Lavoisier.

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 Some Basic Concepts of Chemistry 15

1.5.2 Law of Definite Proportions are produced in a chemical

This law was given by, a reaction they do so in a
French chemist, Joseph simple ratio by volume,
Proust. He stated that a given provided all gases are at
compound always contains the same temperature and
exactly the same proportion of pressure.
elements by weight. Thus, 100 mL of hydrogen Joseph Louis
Proust worked with two Joseph Proust combine with 50 mL of Gay Lussac

samples of cupric carbonate (1754–1826)

oxygen to give 100 mL of
— one of which was of natural water vapour.
origin and the other was synthetic. He found Hydrogen + Oxygen → Water
that the composition of elements present in it 100 mL 50 mL 100 mL
was same for both the samples as shown below: Thus, the volumes of hydrogen and
% of % of % of oxygen which combine (i.e., 100 mL and
copper carbon oxygen 50 mL) bear a simple ratio of 2:1.
Natural Sample 51.35 9.74 38.91 Gay Lussac’s discovery of integer ratio
Synthetic Sample 51.35 9.74 38.91 in volume relationship is actually the law of
definite proportions by volume. The law of
Thus, he concluded that irrespective of the definite proportions, stated earlier, was with
source, a given compound always contains respect to mass. The Gay Lussac’s law was
same elements combined together in the same explained properly by the work of Avogadro
proportion by mass. The validity of this law in 1811.
has been confirmed by various experiments.
It is sometimes also referred to as Law of 1.5.5 Avogadro’s Law
Definite Composition. In 1811, Avogadro proposed that equal
volumes of all gases at the same temperature
1.5.3 Law of Multiple Proportions
and pressure should contain equal number
This law was proposed by Dalton in 1803. of molecules. Avogadro made a distinction
According to this law, if two elements can between atoms and molecules which is
combine to form more than one compound, quite understandable in present times. If
the masses of one element that combine with we consider again the reaction of hydrogen
a fixed mass of the other element, are in the and oxygen to produce water, we see that
ratio of small whole numbers. two volumes of hydrogen combine with one
For example, hydrogen combines with volume of oxygen to give two volumes of water
oxygen to form two compounds, namely, water without leaving any unreacted oxygen.
and hydrogen peroxide.
Note that in the Fig. 1.9 (Page 16) each
Hydrogen + Oxygen → Water box contains equal number of
2g 16g 18g molecules. In fact, Avogadro
Hydrogen + Oxygen → Hydrogen Peroxide could explain the above result
by considering the molecules
2g 32g 34g
to be polyatomic. If hydrogen
Here, the masses of oxygen (i.e., 16 g and 32 g),
which combine with a fixed mass of hydrogen and oxygen were considered
(2g) bear a simple ratio, i.e., 16:32 or 1: 2. as diatomic as recognised
now, then the above results Lorenzo Romano
1.5.4 Gay Lussac’s Law of Gaseous are easily understandable. Amedeo Carlo
Volumes However, Dalton and others Avogadro di
Quareqa edi
This law was given by Gay Lussac in 1808. believed at that time that Carreto
He observed that when gases combine or atoms of the same kind (1776–1856)

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 16 chemistry

Fig. 1.9 Two volumes of hydrogen react with one volume of oxygen to give two volumes of water vapour

cannot combine and molecules of oxygen or Dalton’s theory could explain the laws
hydrogen containing two atoms did not exist. of chemical combination. However, it could
Avogadro’s proposal was published in the not explain the laws of gaseous volumes. It
French Journal de Physique. In spite of being could not provide the reason for combining
correct, it did not gain much support. of atoms, which was answered later by other
After about 50 years, in 1860, the first scientists.
international conference on chemistry was
1.7 Atomic and Molecular Masses
held in Karlsruhe, Germany, to resolve
various ideas. At the meeting, Stanislao After having some idea about the terms
Cannizaro presented a sketch of a course of atoms and molecules, it is appropriate here
chemical philosophy, which emphasised on to understand what do we mean by atomic
the importance of Avogadro’s work. and molecular masses.

1.6 Dalton’s Atomic Theory 1.7.1 Atomic Mass

Although the origin of the idea that matter is The atomic mass or the mass of an atom is
composed of small indivisible particles called actually very-very small because atoms are
‘a-tomio’ (meaning, indivisible), dates back extremely small. Today, we have sophisticated
to the time of Democritus, techniques e.g., mass spectrometry for
a Greek Philosopher (460– determining the atomic masses fairly
370 BC), it again started accurately. But in the nineteenth century,
emerging as a result of several scientists could determine the mass of one
experimental studies which atom relative to another by experimental
led to the laws mentioned means, as has been mentioned earlier.
above. Hydrogen, being the lightest atom was
In 1808, Dalton published John Dalton
arbitrarily assigned a mass of 1 (without
‘A New System of Chemical (1776–1884) any units) and other elements were assigned
Philosophy’, in which he masses relative to it. However, the present
proposed the following : system of atomic masses is based on
1. Matter consists of indivisible atoms. carbon-12 as the standard and has been
agreed upon in 1961. Here, Carbon-12 is
2. All atoms of a given element have identical
one of the isotopes of carbon and can be
properties, including identical mass. Atoms
represented as 12C. In this system, 12C is
of different elements differ in mass.
assigned a mass of exactly 12 atomic mass
3. Compounds are formed when atoms of unit (amu) and masses of all other atoms are
different elements combine in a fixed ratio. given relative to this standard. One atomic
4. Chemical reactions involve reorganisation mass unit is defined as a mass exactly equal
of atoms. These are neither created nor to one-twelfth of the mass of one carbon – 12
destroyed in a chemical reaction. atom.

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 Some Basic Concepts of Chemistry 17

And 1 amu = 1.66056×10–24 g 1.7.3 Molecular Mass

Mass of an atom of hydrogen Molecular mass is the sum of atomic masses
= 1.6736×10–24 g of the elements present in a molecule. It is
obtained by multiplying the atomic mass
Thus, in terms of amu, the mass
of each element by the number of its atoms
of hydrogen atom = and adding them together. For example,
molecular mass of methane, which contains
one carbon atom and four hydrogen atoms,
= 1.0078 amu
can be obtained as follows:
= 1.0080 amu
Molecular mass of methane,
Similarly, the mass of oxygen - 16 (16O) (CH4) = (12.011 u) + 4 (1.008 u)
atom would be 15.995 amu.
= 16.043 u
At present, ‘amu’ has been replaced by
Similarly, molecular mass of water (H2O)
‘u’, which is known as unified mass.
= 2 × atomic mass of hydrogen + 1× atomic
When we use atomic masses of elements
mass of oxygen
in calculations, we actually use average
atomic masses of elements, which are = 2 (1.008 u) + 16.00 u
explained below. = 18.02 u
1.7.2 Average Atomic Mass 1.7.4 Formula Mass
Many naturally occurring elements exist Some substances, such as sodium chloride,
as more than one isotope. When we take do not contain discrete molecules as their
into account the existence of these isotopes constituent units. In such compounds,
and their relative abundance (per cent positive (sodium ion) and negative (chloride ion)
occurrence), the average atomic mass of entities are arranged in a three-dimensional
that element can be computed. For example, structure, as shown in Fig. 1.10.
carbon has the following three isotopes with
relative abundances and masses as shown
against each of them.
Isotope Relative Atomic Mass
Abundance (amu)
(%)

12
C 98.892 12
13
C 1.108 13.00335
14
C 2 ×10–10 14.00317
Fig. 1.10 Packing of Na+ and Cl– ions
From the above data, the average atomic in sodium chloride
mass of carbon will come out to be:
(0.98892) (12 u) + (0.01108) (13.00335 u) + It may be noted that in sodium chloride,
(2 × 10–12) (14.00317 u) = 12.011 u one Na+ ion is surrounded by six Cl– ion and
Similarly, average atomic masses for vice-versa.
other elements can be calculated. In the The formula, such as NaCl, is used to
periodic table of elements, the atomic masses calculate the formula mass instead of
mentioned for different elements actually molecular mass as in the solid state sodium
represent their average atomic masses. chloride does not exist as a single entity.

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 18 chemistry

Thus, the formula mass of sodium chloride is This number of entities in 1 mol is so
atomic mass of sodium + atomic mass of chlorine important that it is given a separate name and
= 23.0 u + 35.5 u = 58.5 u symbol. It is known as ‘Avogadro constant’,
or Avogadro number denoted by NA in honour
Problem 1.1 of Amedeo Avogadro. To appreciate the
Calculate the molecular mass of glucose largeness of this number, let us write it with
(C6H12O6) molecule. all zeroes without using any powers of ten.
Solution 602213670000000000000000
Molecular mass of glucose (C6H12O6) Hence, so many entities (atoms, molecules or
= 6 (12.011 u) + 12 (1.008 u) + any other particle) constitute one mole of a
6 (16.00 u) particular substance.
= (72.066 u) + (12.096 u) + We can, therefore, say that 1 mol of hydrogen
(96.00 u) atoms = 6.022 × 1023 atoms
= 180.162 u
1 mol of water molecules = 6.022 × 1023 water
1.8 Mole concept and Molar Masses molecules
Atoms and molecules are extremely small 1 mol of sodium chloride = 6.022 ×1023 formula
in size and their numbers in even a small units of sodium chloride
amount of any substance is really very large.
To handle such large numbers, a unit of Having defined the mole, it is easier to
convenient magnitude is required. know the mass of one mole of a substance
Just as we denote one dozen for 12 items, or the constituent entities. The mass of one
score for 20 items, gross for 144 items, we mole of a substance in grams is called its
use the idea of mole to count entities at the molar mass. The molar mass in grams is
microscopic level (i.e., atoms, molecules, numerically equal to atomic/molecular/
particles, electrons, ions, etc). formula mass in u.
In SI system, mole (symbol, mol) was
introduced as seventh base quantity for the Molar mass of water = 18.02 g mol–1
amount of a substance. Molar mass of sodium chloride = 58.5 g mol–1
The mole, symbol mol, is the SI unit of
amount of substance. One mole contains 1.9 Percentage Composition
exactly 6.02214076 × 1023 elementary entities. So far, we were dealing with the number of
This number is the fixed numerical value of entities present in a given sample. But many
the Avogadro constant, NA, when expressed a time, information regarding the percentage
in the unit mol–1 and is called the Avogadro of a particular element present in a compound
number. The amount of substance, symbol is required. Suppose, an unknown or new
n, of a system is a measure of the number of compound is given to you, the first question
specified elementary entities. An elementary
entity may be an atom, a molecule, an ion,
an electron, any other particle or specified
group of particles. It may be emphasised that
the mole of a substance always contains the
same number of entities, no matter what the
substance may be. In order to determine this
number precisely, the mass of a carbon–12
atom was determined by a mass spectrometer
and found to be equal to 1.992648 × 10–23 g.
Knowing that one mole of carbon weighs 12 g,
the number of atoms in it is equal to:
12 g / mol 12C
1.992648  10 23 g /12 C atom
 6.0221367  1023 atoms/mol Fig. 1.11 One mole of various substances

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 Some Basic Concepts of Chemistry 19

you would ask is: what is its formula or what 1.9.1 Empirical Formula for Molecular
are its constituents and in what ratio are they Formula
present in the given compound? For known An empirical formula represents the simplest
compounds also, such information provides a whole number ratio of various atoms present
check whether the given sample contains the in a compound, whereas, the molecular
same percentage of elements as present in a formula shows the exact number of different
pure sample. In other words, one can check types of atoms present in a molecule of a
the purity of a given sample by analysing this compound.
data.
If the mass per cent of various elements
Let us understand it by taking the example present in a compound is known, its empirical
of water (H2O). Since water contains hydrogen formula can be determined. Molecular formula
and oxygen, the percentage composition of can further be obtained if the molar mass is
both these elements can be calculated as known. The following example illustrates
follows: this sequence.
Mass % of an element =
mass of that element in the compound × 100
molar mass of the compound Problem 1.2
A compound contains 4.07% hydrogen,
Molar mass of water = 18.02 g 24.27% carbon and 71.65% chlorine.
Mass % of hydrogen = Its molar mass is 98.96 g. What are its
empirical and molecular formulas?
= 11.18 Solution
16.00
Mass % of oxygen = × 100 Step 1. Conversion of mass per cent
18.02 to grams
= 88.79
Since we are having mass per cent, it is
Let us take one more example. What is the convenient to use 100 g of the compound
percentage of carbon, hydrogen and oxygen as the starting material. Thus, in the
in ethanol? 100 g sample of the above compound,
Molecular formula of ethanol is: C2H5OH 4.07g hydrogen, 24.27g carbon and
71.65g chlorine are present.
Molar mass of ethanol is:
(2×12.01 + 6×1.008 + 16.00) g = 46.068 g Step 2. Convert into number moles of
each element
Mass per cent of carbon
24.02 g Divide the masses obtained above by
= × 100 = 52.14% respective atomic masses of various
46.068 g elements. This gives the number of
Mass per cent of hydrogen moles of constituent elements in the
6.048 g compound
= × 100 = 13.13%
46.068 g 4.07 g
Moles of hydrogen = = 4.04
Mass per cent of oxygen 1.008 g
16.00 g 24.27 g
= × 100 = 34.73% Moles of carbon = = 2.021
46.068 g 12.01 g
After understanding the calculation of 71.65 g
per cent of mass, let us now see what Moles of chlorine = = 2.021
information can be obtained from the 35.453 g
per cent composition data.

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 20 chemistry

equation of a given reaction. Let us consider

Step 3. Divide each of the mole values the combustion of methane. A balanced
obtained above by the smallest number equation for this reaction is as given below:
amongst them
CH4 (g) + 2O2 (g) → CO2 (g) + 2 H2O (g)
Since 2.021 is smallest value, division Here, methane and dioxygen are called
by it gives a ratio of [Link] for H:C:Cl. reactants and carbon dioxide and water are
In case the ratios are not whole numbers, called products. Note that all the reactants
then they may be converted into whole and the products are gases in the above
number by multiplying by the suitable reaction and this has been indicated by
coefficient. letter (g) in the brackets next to its formula.
Step 4. Write down the empirical Similarly, in case of solids and liquids, (s) and
formula by mentioning the numbers (l) are written respectively.
after writing the symbols of respective The coefficients 2 for O 2 and H2O are
elements called stoichiometric coefficients. Similarly
CH2Cl is, thus, the empirical formula the coefficient for CH4 and CO2 is one in each
of the above compound. case. They represent the number of molecules
(and moles as well) taking part in the reaction
Step 5. Writing molecular formula
or formed in the reaction.
(a) Determine empirical formula mass by
Thus, according to the above chemical
adding the atomic masses of various
atoms present in the empirical formula. reaction,
For CH2Cl, empirical formula mass is • One mole of CH4(g) reacts with two moles
12.01 + (2 ×1.008) + 35.453 of O2(g) to give one mole of CO2(g) and
= 49.48 g two moles of H2O(g)
(b) Divide Molar mass by empirical • One molecule of CH 4 (g) reacts with
formula mass
2 molecules of O2(g) to give one molecule
of CO2(g) and 2 molecules of H2O(g)
• 22.7 L of CH4(g) reacts with 45.4 L of O2
= 2 = (n) (g) to give 22.7 L of CO2 (g) and 45.4 L of
(c) Multiply empirical formula by n H2O(g)
obtained above to get the molecular • 16 g of CH4 (g) reacts with 2×32 g of O2
formula
(g) to give 44 g of CO2 (g) and 2×18 g of
Empirical formula = CH2Cl, n = 2. Hence H2O (g).
molecular formula is C2H4Cl2.
From these relationships, the given data can
be interconverted as follows:
1.10 Stoichiometry and
mass
Stoichiometric Calculations
The word ‘stoichiometry’ is derived from
two Greek words — stoicheion (meaning, Mass
= Density
element) and metron (meaning, measure). Volume
Stoichiometry, thus, deals with the calculation
of masses (sometimes volumes also) of the 1.10.1 Limiting Reagent
reactants and the products involved in a Many a time, reactions are carried out with
chemical reaction. Before understanding how the amounts of reactants that are different
to calculate the amounts of reactants required than the amounts as required by a balanced
or the products produced in a chemical chemical reaction. In such situations, one
reaction, let us study what information reactant is in more amount than the amount
is available from the balanced chemical required by balanced chemical reaction. The

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 Some Basic Concepts of Chemistry 21

reactant which is present in the least amount important to understand as how the amount
gets consumed after sometime and after that of substance is expressed when it is present in
further reaction does not take place whatever the solution. The concentration of a solution
be the amount of the other reactant. Hence, or the amount of substance present in its
the reactant, which gets consumed first, given volume can be expressed in any of the
limits the amount of product formed and is, following ways.
therefore, called the limiting reagent. 1. Mass per cent or weight per cent (w/w %)
In performing stoichiometric calculations, 2. Mole fraction
this aspect is also to be kept in mind. 3. Molarity
1.10.2 Reactions in Solutions 4. Molality
A majority of reactions in the laboratories Let us now study each one of them in
are carried out in solutions. Therefore, it is detail.

Balancing a chemical equation

According to the law of conservation of mass, a balanced chemical equation has the same number of
atoms of each element on both sides of the equation. Many chemical equations can be balanced by
trial and error. Let us take the reactions of a few metals and non-metals with oxygen to give oxides
4 Fe(s) + 3O2(g) → 2Fe2O3(s) (a) balanced equation
2 Mg(s) + O2(g) → 2MgO(s) (b) balanced equation
P4(s) + O2 (g) → P4O10(s) (c) unbalanced equation
Equations (a) and (b) are balanced, since there are same number of metal and oxygen atoms on
each side of the equations. However equation (c) is not balanced. In this equation, phosphorus
atoms are balanced but not the oxygen atoms. To balance it, we must place the coefficient 5 on
the left of oxygen on the left side of the equation to balance the oxygen atoms appearing on the
right side of the equation.
P4(s) + 5O2(g) → P4O10(s) balanced equation
Now, let us take combustion of propane, C3H8. This equation can be balanced in steps.
Step 1 Write down the correct formulas of reactants and products. Here, propane and oxygen are
reactants, and carbon dioxide and water are products.
C3H8(g) + O2(g) → CO2 (g) + H2O(l) unbalanced equation
Step 2 Balance the number of C atoms: Since 3 carbon atoms are in the reactant, therefore, three
CO2 molecules are required on the right side.
C3H8 (g) + O2 (g) → 3CO2 (g) + H2O (l)
Step 3 Balance the number of H atoms: on the left there are 8 hydrogen atoms in the reactants
however, each molecule of water has two hydrogen atoms, so four molecules of water will be
required for eight hydrogen atoms on the right side.
C3H8 (g) +O2 (g) → 3CO2 (g)+4H2O (l)
Step 4 Balance the number of O atoms: There are 10 oxygen atoms on the right side (3 × 2 = 6 in
CO2 and 4×1= 4 in water). Therefore, five O2 molecules are needed to supply the required 10 CO2
and 4×1= 4 in water). Therefore, five O2 molecules are needed to supply the required 10 oxygen
atoms.
C3H8 (g) +5O2 (g) → 3CO2 (g) + 4H2O (l)
Step 5 Verify that the number of atoms of each element is balanced in the final equation. The
equation shows three carbon atoms, eight hydrogen atoms, and 10 oxygen atoms on each side.
All equations that have correct formulas for all reactants and products can be balanced. Always
remember that subscripts in formulas of reactants and products cannot be changed to balance
an equation.

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 22 chemistry

Problem 1.3 the limiting reagent in the production of

NH3 in this situation.
Calculate the amount of water (g)
produced by the combustion of 16 g Solution
of methane.
A balanced equation for the above
Solution reaction is written as follows :
The balanced equation for the
combustion of methane is :
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) Calculation of moles :
(i) 16 g of CH4 corresponds to one mole. Number of moles of N2
(ii) From the above equation, 1 mol of 1000 g N 2 1 mol N 2
CH4 (g) gives 2 mol of H2O (g). = 50.0 kg N 2 × ×
1 kg N 2 28.0 g N 2
2 mol of water (H2O) = 2×(2+16)
= 2×18 = 36 g = 17.86×102 mol
Number of moles of H2
18 g H2O
1 mol H2O = 18 g H2O ⇒ =1 1000 g H2 1 mol H2
1mol H2O = 10.00 kg H2 × ×
1 kg H2 2.016 g H2
18 g H2O = 4.96 × 103 mol
Hence, 2 mol H2O×
1mol H2O According to the above equation, 1
mol N2 (g) requires 3 mol H2 (g), for the
= 2×18 g H2O = 36 g H2O reaction. Hence, for 17.86×102 mol of
Problem 1.4 N2, the moles of H2 (g) required would be
How many moles of methane are 3 mol H2  g 
required to produce 22g CO2 (g) after 17.86  102 mol N 2 
1 mol N 2  g 
combustion?
= 5.36 × 10 mol H2
3
Solution
But we have only 4.96×10 3 mol H 2.
According to the chemical equation, Hence, dihydrogen is the limiting
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) reagent in this case. So, NH3(g) would
44g CO2 (g) is obtained from 16 g CH4 (g). be formed only from that amount of
available dihydrogen i.e., 4.96 × 103 mol
[∴ 1 mol CO2(g) is obtained from 1 mol
of CH4(g)] Since 3 mol H2(g) gives 2 mol NH3(g)
Number of moles of CO2 (g) 2 mol NH3  g 
1 mol CO2  g  4.96 ×103 mol H2 (g) ×
= 22 g CO2 (g) × 3 mol H2  g 
44 g CO2  g 
= 3.30 × 103 mol NH3 (g)
= 0.5 mol CO2 (g)
Hence, 0.5 mol CO 2 (g) would be 3.30 × 103 mol NH3 (g) is obtained.
obtained from 0.5 mol CH4 (g) or 0.5 mol If they are to be converted to grams, it
of CH4 (g) would be required to produce is done as follows :
22 g CO2 (g).
1 mol NH3 (g) = 17.0 g NH3 (g)
Problem 1.5
17.0 g NH3  g 
50.0 kg of N2 (g) and 10.0 kg of H2 (g) 3.30 ×103 mol NH3 (g) ×
are mixed to produce NH3 (g). Calculate 1 mol NH3  g 
the amount of NH3 (g) formed. Identify

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 Some Basic Concepts of Chemistry 23

3. Molarity
= 3.30×103×17 g NH3 (g)
It is the most widely used unit and is denoted
= 56.1×103 g NH3 by M. It is defined as the number of moles of
= 56.1 kg NH3 the solute in 1 litre of the solution. Thus,
No. of moles of solute
1. Mass per cent Molarity (M) =
Volume of solution in litres
It is obtained by using the following relation: Suppose, we have 1 M solution of a
substance, say NaOH, and we want to prepare
a 0.2 M solution from it.
1 M NaOH means 1 mol of NaOH present
in 1 litre of the solution. For 0.2 M solution,
Problem 1.6 we require 0.2 moles of NaOH dissolved in
A solution is prepared by adding 2 g of a 1 litre solution.
substance A to 18 g of water. Calculate Hence, for making 0.2M solution from 1M
the mass per cent of the solute. solution, we have to take that volume of 1M
Solution NaOH solution, which contains 0.2 mol of NaOH
and dilute the solution with water to 1 litre.
Now, how much volume of concentrated
(1M) NaOH solution be taken, which contains
0.2 moles of NaOH can be calculated as follows:
If 1 mol is present in 1L or 1000 mL
solution
then, 0.2 mol is present in
1000 mL
× 0.2 mol solution
1 mol
2. Mole Fraction
It is the ratio of number of moles of a = 200 mL solution
particular component to the total number Thus, 200 mL of 1M NaOH are taken and
of moles of the solution. If a substance ‘A’ enough water is added to dilute it to make it 1 litre.
dissolves in substance ‘B’ and their number In fact for such calculations, a general
of moles are nA and nB, respectively, then the formula, M1×V1 = M2 × V2 where M and V are
mole fractions of A and B are given as: molarity and volume, respectively, can be used.
In this case, M1 is equal to 0.2M; V1 = 1000
mL and, M2 = 1.0M; V2 is to be calculated.
Substituting the values in the formula:
0.2 M × 1000 mL = 1.0 M × V2

Note that the number of moles of solute

(NaOH) was 0.2 in 200 mL and it has remained
the same, i.e., 0.2 even after dilution ( in 1000
mL) as we have changed just the amount
of solvent (i.e., water) and have not done
anything with respect to NaOH. But keep in
mind the concentration.

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 24 chemistry

Problem 1.7 Problem 1.8

Calculate the molarity of NaOH in the The density of 3 M solution of NaCl is
solution prepared by dissolving its 4 g 1.25 g mL–1. Calculate the molality of
in enough water to form 250 mL of the the solution.
solution.
Solution
Solution M = 3 mol L–1
Since molarity (M) Mass of NaCl
in 1 L solution = 3 × 58.5 = 175.5 g
Mass of
1L solution = 1000 × 1.25 = 1250 g
(since density = 1.25 g mL–1)
Mass of water in solution = 1250 –75.5
= 1074.5 g
No. of moles of solute
Molality =
Mass of solvent in kg
3 mol
= = 2.79 m
Note that molarity of a solution depends 1.0745 kg
upon temperature because volume of a Often in a chemistry laboratory, a
solution is temperature dependent. solution of a desired concentration is
prepared by diluting a solution of known
4. Molality higher concentration. The solution of
higher concentration is also known as
It is defined as the number of moles of solute stock solution. Note that the molality
present in 1 kg of solvent. It is denoted by m. of a solution does not change with
No. of moles of solute temperature since mass remains
Thus, Molality (m) = unaffected with temperature.
Mass of solvent in kg

Summary

Chemistry, as we understand it today is not a very old discipline. People in ancient India,
already had the knowledge of many scientific phenomenon much before the advent of
modern science. They applied the knowledge in various walks of life.

The study of chemistry is very important as its domain encompasses every sphere
of life. Chemists study the properties and structure of substances and the changes
undergone by them. All substances contain matter, which can exist in three states –
solid, liquid or gas. The constituent particles are held in different ways in these states
of matter and they exhibit their characteristic properties. Matter can also be classified
into elements, compounds or mixtures. An element contains particles of only one type,
which may be atoms or molecules. The compounds are formed where atoms of two or
more elements combine in a fixed ratio to each other. Mixtures occur widely and many
of the substances present around us are mixtures.

When the properties of a substance are studied, measurement is inherent. The

quantification of properties requires a system of measurement and units in which the
quantities are to be expressed. Many systems of measurement exist, of which the English

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 Some Basic Concepts of Chemistry 25

and the Metric Systems are widely used. The scientific community, however, has agreed to
have a uniform and common system throughout the world, which is abbreviated as SI units
(International System of Units).
Since measurements involve recording of data, which are always associated with a certain
amount of uncertainty, the proper handling of data obtained by measuring the quantities
is very important. The measurements of quantities in chemistry are spread over a wide
range of 10–31 to 10+23. Hence, a convenient system of expressing the numbers in scientific
notation is used. The uncertainty is taken care of by specifying the number of significant
figures, in which the observations are reported. The dimensional analysis helps to express
the measured quantities in different systems of units. Hence, it is possible to interconvert
the results from one system of units to another.
The combination of different atoms is governed by basic laws of chemical combination
— these being the Law of Conservation of Mass, Law of Definite Proportions, Law of
Multiple Proportions, Gay Lussac’s Law of Gaseous Volumes and Avogadro Law. All
these laws led to the Dalton’s atomic theory, which states that atoms are building blocks
of matter. The atomic mass of an element is expressed relative to 12C isotope of carbon,
which has an exact value of 12u. Usually, the atomic mass used for an element is the
average atomic mass obtained by taking into account the natural abundance of different
isotopes of that element. The molecular mass of a molecule is obtained by taking sum of
the atomic masses of different atoms present in a molecule. The molecular formula can be
calculated by determining the mass per cent of different elements present in a compound
and its molecular mass.
The number of atoms, molecules or any other particles present in a given system are
expressed in the terms of Avogadro constant (6.022 × 1023). This is known as 1 mol of the
respective particles or entities.
Chemical reactions represent the chemical changes undergone by different elements and
compounds. A balanced chemical equation provides a lot of information. The coefficients
indicate the molar ratios and the respective number of particles taking part in a particular
reaction. The quantitative study of the reactants required or the products formed is called
stoichiometry. Using stoichiometric calculations, the amount of one or more reactant(s)
required to produce a particular amount of product can be determined and vice-versa. The
amount of substance present in a given volume of a solution is expressed in number of ways,
e.g., mass per cent, mole fraction, molarity and molality.

exerciseS

1.1 Calculate the molar mass of the following:

(i) H2O (ii) CO2 (iii) CH4
1.2 Calculate the mass per cent of different elements present in sodium sulphate
(Na2SO4).
1.3 Determine the empirical formula of an oxide of iron, which has 69.9% iron and
30.1% dioxygen by mass.
1.4 Calculate the amount of carbon dioxide that could be produced when
(i) 1 mole of carbon is burnt in air.
(ii) 1 mole of carbon is burnt in 16 g of dioxygen.
(iii) 2 moles of carbon are burnt in 16 g of dioxygen.
1.5 Calculate the mass of sodium acetate (CH3COONa) required to make 500 mL of
0.375 molar aqueous solution. Molar mass of sodium acetate is 82.0245 g mol–1.

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 26 chemistry

1.6 Calculate the concentration of nitric acid in moles per litre in a sample which has
a density, 1.41 g mL–1 and the mass per cent of nitric acid in it being 69%.
1.7 How much copper can be obtained from 100 g of copper sulphate (CuSO4)?
1.8 Determine the molecular formula of an oxide of iron, in which the mass per cent of
iron and oxygen are 69.9 and 30.1, respectively.
1.9 Calculate the atomic mass (average) of chlorine using the following data:
% Natural Abundance Molar Mass
35
Cl 75.77 34.9689
37
Cl 24.23 36.9659
1.10 In three moles of ethane (C2H6), calculate the following:
(i) Number of moles of carbon atoms.
(ii) Number of moles of hydrogen atoms.
(iii) Number of molecules of ethane.
1.11 What is the concentration of sugar (C12H22O11) in mol L–1 if its 20 g are dissolved in
enough water to make a final volume up to 2L?
1.12 If the density of methanol is 0.793 kg L–1, what is its volume needed for making 2.5
L of its 0.25 M solution?
1.13 Pressure is determined as force per unit area of the surface. The SI unit of pressure,
pascal is as shown below:
1Pa = 1N m–2
If mass of air at sea level is 1034 g cm–2, calculate the pressure in pascal.
1.14 What is the SI unit of mass? How is it defined?
1.15 Match the following prefixes with their multiples:
Prefixes Multiples
(i) micro 106
(ii) deca 109
(iii) mega 10–6
(iv) giga 10–15
(v) femto 10
1.16 What do you mean by significant figures?
1.17 A sample of drinking water was found to be severely contaminated with chloroform,
CHCl3, supposed to be carcinogenic in nature. The level of contamination was 15
ppm (by mass).
(i) Express this in per cent by mass.
(ii) Determine the molality of chloroform in the water sample.
1.18 Express the following in the scientific notation:
(i) 0.0048
(ii) 234,000
(iii) 8008
(iv) 500.0
(v) 6.0012
1.19 How many significant figures are present in the following?
(i) 0.0025
(ii) 208
(iii) 5005

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 Some Basic Concepts of Chemistry 27

(iv) 126,000
(v) 500.0
(vi) 2.0034
1.20 Round up the following upto three significant figures:
(i) 34.216
(ii) 10.4107
(iii) 0.04597
(iv) 2808
1.21 The following data are obtained when dinitrogen and dioxygen react together to form
different compounds:
Mass of dinitrogen Mass of dioxygen
(i) 14 g 16 g
(ii) 14 g 32 g
(iii) 28 g 32 g
(iv) 28 g 80 g
(a) Which law of chemical combination is obeyed by the above experimental data? Give
its statement.
(b) Fill in the blanks in the following conversions:
(i) 1 km = ...................... mm = ...................... pm
(ii) 1 mg = ...................... kg = ...................... ng
(iii) 1 mL = ...................... L = ...................... dm3
1.22 If the speed of light is 3.0 × 108 m s–1, calculate the distance covered by light in
2.00 ns.
1.23 In a reaction
A + B2  AB2
Identify the limiting reagent, if any, in the following reaction mixtures.
(i) 300 atoms of A + 200 molecules of B
(ii) 2 mol A + 3 mol B
(iii) 100 atoms of A + 100 molecules of B
(iv) 5 mol A + 2.5 mol B
(v) 2.5 mol A + 5 mol B
1.24 Dinitrogen and dihydrogen react with each other to produce ammonia according to
the following chemical equation:
N2 (g) + H2 (g)  2NH3 (g)
(i) Calculate the mass of ammonia produced if 2.00 × 103 g dinitrogen reacts
with 1.00 × 103 g of dihydrogen.
(ii) Will any of the two reactants remain unreacted?
(iii) If yes, which one and what would be its mass?
1.25 How are 0.50 mol Na2CO3 and 0.50 M Na2CO3 different?
1.26 If 10 volumes of dihydrogen gas reacts with five volumes of dioxygen gas, how many
volumes of water vapour would be produced?
1.27 Convert the following into basic units:
(i) 28.7 pm
(ii) 15.15 pm
(iii) 25365 mg

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 28 chemistry

1.28 Which one of the following will have the largest number of atoms?
(i) 1 g Au (s)
(ii) 1 g Na (s)
(iii) 1 g Li (s)
(iv) 1 g of Cl2(g)
1.29 Calculate the molarity of a solution of ethanol in water, in which the mole fraction of
ethanol is 0.040 (assume the density of water to be one).
1.30 What will be the mass of one 12
C atom in g?
1.31 How many significant figures should be present in the answer of the following
calculations?
0.02856 × 298.15 × 0.112
(i) (ii) 5 × 5.364
0.5785
(iii) 0.0125 + 0.7864 + 0.0215
1.32 Use the data given in the following table to calculate the molar mass of naturally occuring
argon isotopes:
Isotope Isotopic molar mass Abundance
36
Ar 35.96755 g mol–1 0.337%
38
Ar 37.96272 g mol–1 0.063%
40
Ar 39.9624 g mol –1
99.600%
1.33 Calculate the number of atoms in each of the following (i) 52 moles of Ar (ii) 52 u of He
(iii) 52 g of He.
1.34 A welding fuel gas contains carbon and hydrogen only. Burning a small sample of it in
oxygen gives 3.38 g carbon dioxide, 0.690 g of water and no other products. A volume
of 10.0 L (measured at STP) of this welding gas is found to weigh 11.6 g. Calculate
(i) empirical formula, (ii) molar mass of the gas, and (iii) molecular formula.
1.35 Calcium carbonate reacts with aqueous HCl to give CaCl2 and CO2 according to the
reaction, CaCO3 (s) + 2 HCl (aq) → CaCl2 (aq) + CO2(g) + H2O(l)
What mass of CaCO3 is required to react completely with 25 mL of 0.75 M HCl?
1.36 Chlorine is prepared in the laboratory by treating manganese dioxide (MnO2) with
aqueous hydrochloric acid according to the reaction
4 HCl (aq) + MnO2(s) → 2H2O (l) + MnCl2(aq) + Cl2 (g)
How many grams of HCl react with 5.0 g of manganese dioxide?

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 Unit 2

structure of atom

The rich diversity of chemical behaviour of different

Objectives elements can be traced to the differences in the internal

structure of atoms of these elements.

After studying this unit you will be

able to
• know about the discovery of The existence of atoms has been proposed since the time
electron, proton and neutron and of early Indian and Greek philosophers (400 B.C.) who
their characteristics; were of the view that atoms are the fundamental building
• describe Thomson, Rutherford blocks of matter. According to them, the continued
and Bohr atomic models; subdivisions of matter would ultimately yield atoms
which would not be further divisible. The word ‘atom’
• understand the important features
has been derived from the Greek word ‘a-tomio’ which
of the quantum mechanical model
means ‘uncut-able’ or ‘non-divisible’. These earlier ideas
of atom;
were mere speculations and there was no way to test
• understand nature of them experimentally. These ideas remained dormant for
electromagnetic radiation and a very long time and were revived again by scientists in
Planck’s quantum theory; the nineteenth century.
• explain the photoelectric effect The atomic theory of matter was first proposed
and describe features of atomic on a firm scientific basis by John Dalton, a British
spectra; school teacher in 1808. His theory, called Dalton’s
• state the de Broglie relation and atomic theory, regarded the atom as the ultimate
Heisenberg uncertainty principle; particle of matter (Unit 1). Dalton’s atomic theory was
able to explain the law of conservation of mass, law of
• define an atomic orbital in terms
constant composition and law of multiple proportion
of quantum numbers;
very successfully. However, it failed to explain the results
• state aufbau principle, Pauli of many experiments, for example, it was known that
exclusion principle and Hund’s substances like glass or ebonite when rubbed with silk
rule of maximum multiplicity; and or fur get electrically charged.
• write the electronic configurations In this unit we start with the experimental observations
of atoms. made by scientists towards the end of nineteenth and
beginning of twentieth century. These established that
atoms are made of sub-atomic particles, i.e., electrons,
protons and neutrons — a concept very different from
that of Dalton.

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 30 chemistry

2.1 Discovery of Sub-atomic

Particles
An insight into the structure of atom was
obtained from the experiments on electrical
discharge through gases. Before we discuss
these results we need to keep in mind a
basic rule regarding the behaviour of charged
particles : “Like charges repel each other and
unlike charges attract each other”. Fig. 2.1(a) A cathode ray discharge tube

2.1.1 Discovery of Electron

In 1830, Michael Faraday showed that if
electricity is passed through a solution of an
electrolyte, chemical reactions occurred at the
electrodes, which resulted in the liberation
and deposition of matter at the electrodes.
He formulated certain laws which you will
study in Class XII. These results suggested
the particulate nature of electricity.
Fig. 2.1(b) A cathode ray discharge tube with
In mid 1850s many scientists mainly perforated anode
Faraday began to study electrical discharge
in partially evacuated tubes, known as The results of these experiments are
cathode ray discharge tubes. It is depicted summarised below.
in Fig. 2.1. A cathode ray tube is made of (i) The cathode rays start from cathode and
move towards the anode.
glass containing two thin pieces of metal,
called electrodes, sealed in it. The electrical (ii) These rays themselves are not visible
but their behaviour can be observed
discharge through the gases could be
with the help of certain kind of materials
observed only at very low pressures and at (fluorescent or phosphorescent) which
very high voltages. The pressure of different glow when hit by them. Television
gases could be adjusted by evacuation of the picture tubes are cathode ray tubes
glass tubes. When sufficiently high voltage and television pictures result due to
is applied across the electrodes, current fluorescence on the television screen
starts flowing through a stream of particles coated with certain fluorescent or
moving in the tube from the negative phosphorescent materials.
electrode (cathode) to the positive electrode (iii) In the absence of electrical or magnetic
field, these rays travel in straight lines
(anode). These were called cathode rays or
(Fig. 2.2).
cathode ray particles. The flow of current
(iv) In the presence of electrical or magnetic
from cathode to anode was further checked
field, the behaviour of cathode rays are
by making a hole in the anode and coating
similar to that expected from negatively
the tube behind anode with phosphorescent charged particles, suggesting that
material zinc sulphide. When these rays, the cathode rays consist of negatively
after passing through anode, strike the zinc charged particles, called electrons.
sulphide coating, a bright spot is developed (v) The characteristics of cathode rays
on the coating [Fig. 2.1(b)]. (electrons) do not depend upon the

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 structure of atom 31

material of electrodes and the nature of (iii) the strength of the electrical or magnetic
the gas present in the cathode ray tube. field — the deflection of electrons from its
Thus, we can conclude that electrons are original path increases with the increase
basic constituent of all the atoms. in the voltage across the electrodes, or
the strength of the magnetic field.
2.1.2 Charge to Mass Ratio of Electron
By carrying out accurate measurements
In 1897, British physicist J.J. Thomson on the amount of deflections observed by
measured the ratio of electrical charge (e) to the electrons on the electric field strength or
the mass of electron (me ) by using cathode magnetic field strength, Thomson was able to
ray tube and applying electrical and magnetic determine the value of e/me as:
field perpendicular to each other as well as
to the path of electrons (Fig. 2.2). When only = 1.758820 × 1011 C kg–1 (2.1)
electric field is applied, the electrons deviate
from their path and hit the cathode ray tube Where me is the mass of the electron in kg
at point A (Fig. 2.2). Similarly when only and e is the magnitude of the charge on the
magnetic field is applied, electron strikes electron in coulomb (C). Since electrons are
the cathode ray tube at point C. By carefully negatively charged, the charge on electron
balancing the electrical and magnetic field is –e.
strength, it is possible to bring back the
electron to the path which is followed in the 2.1.3 Charge on the Electron
absence of electric or magnetic field and they R.A. Millikan (1868-1953) devised a method
hit the screen at point B. Thomson argued known as oil drop experiment (1906-14),
that the amount of deviation of the particles to determine the charge on the electrons.
from their path in the presence of electrical He found the charge on the electron to be
or magnetic field depends upon: – 1.6 × 10–19 C. The present accepted value of
electrical charge is – 1.602176 × 10–19 C. The
(i) the magnitude of the negative charge on
mass of the electron (me) was determined by
the particle, greater the magnitude of
combining these results with Thomson’s value
the charge on the particle, greater is the
of e/me ratio.
interaction with the electric or magnetic
field and thus greater is the deflection.
(ii) the mass of the particle — lighter the
particle, greater the deflection. = 9.1094×10–31 kg (2.2)

Fig. 2.2 The apparatus to determine the charge to the mass ratio of electron

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 32 chemistry

2.1.4 Discovery of Protons and Neutrons

Millikan’s Oil Drop Method
Electrical discharge carried out in the modified
cathode ray tube led to the discovery of canal In this method, oil droplets in the form of
rays carrying positively charged particles. The mist, produced by the atomiser, were allowed
characteristics of these positively charged to enter through a tiny hole in the upper
particles are listed below. plate of electrical condenser. The downward
motion of these droplets was viewed through
(i) Unlike cathode rays, mass of positively the telescope, equipped with a micrometer
charged particles depends upon the eye piece. By measuring the rate of fall of
nature of gas present in the cathode these droplets, Millikan was able to measure
ray tube. These are simply the positively the mass of oil droplets. The air inside the
charged gaseous ions. chamber was ionized by passing a beam of
(ii) The charge to mass ratio of the particles X-rays through it. The electrical charge on
depends on the gas from which these these oil droplets was acquired by collisions
with gaseous ions. The fall of these charged
originate.
oil droplets can be retarded, accelerated or
(iii) Some of the positively charged particles made stationary depending upon the charge
carry a multiple of the fundamental unit on the droplets and the polarity and strength
of electrical charge. of the voltage applied to the plate. By
(iv) The behaviour of these particles in the carefully measuring the effects of electrical
magnetic or electrical field is opposite field strength on the motion of oil droplets,
to that observed for electron or cathode Millikan concluded that the magnitude of
electrical charge, q, on the droplets is always
rays.
an integral multiple of the electrical charge,
The smallest and lightest positive ion e, that is, q = n e, where n = 1, 2, 3... .
was obtained from hydrogen and was called
proton. This positively charged particle was
characterised in 1919. Later, a need was felt
for the presence of electrically neutral particle
as one of the constituent of atom. These
particles were discovered by Chadwick (1932)
by bombarding a thin sheet of beryllium
by α-particles. When electrically neutral
particles having a mass slightly greater than
that of protons were emitted. He named
these particles as neutrons. The important
properties of all these fundamental particles
are given in Table 2.1.
Fig. 2.3 The Millikan oil drop apparatus for
2.2 Atomic Models measuring charge ‘e’. In chamber,
Observations obtained from the experiments the forces acting on oil drop are:
mentioned in the previous sections have gravitational, electrostatic due to
electrical field and a viscous drag
suggested that Dalton’s indivisible atom is
force when the oil drop is moving.
composed of sub-atomic particles carrying
positive and negative charges. The major
problems before the scientists after the • to explain the formation of different
discovery of sub-atomic particles were: kinds of molecules by the combination of
different atoms and,
• to account for the stability of atom,
• to compare the behaviour of elements • to understand the origin and nature of
the characteristics of electromagnetic
in terms of both physical and chemical
radiation absorbed or emitted by atoms.
properties,

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 structure of atom 33

Table 2.1 Properties of Fundamental Particles

Name Symbol Absolute Relative Mass/kg Mass/u Approx.

charge/C charge mass/u

Electron e – 1.602176×10–19 –1 9.109382×10–31 0.00054 0

Proton p + 1.602176×10–19 +1 1.6726216×10–27 1.00727 1

Neutron n 0 0 1.674927×10–27 1.00867 1

Different atomic models were proposed

to explain the distributions of these charged In the later half of the nineteenth century
particles in an atom. Although some of these different kinds of rays were discovered,
models were not able to explain the stability besides those mentioned earlier. Wilhalm
of atoms, two of these models, one proposed Röentgen (1845-1923) in 1895 showed
by J.J. Thomson and the other proposed by that when electrons strike a material in
Ernest Rutherford are discussed below. the cathode ray tubes, produce rays which
can cause fluorescence in the fluorescent
2.2.1 Thomson Model of Atom
materials placed outside the cathode ray
J. J. Thomson, in 1898, proposed that an
tubes. Since Röentgen did not know the
atom possesses a spherical shape (radius
nature of the radiation, he named them
approximately 10–10 m) in which the positive
X-rays and the name is still carried on. It was
charge is uniformly distributed. The electrons
noticed that X-rays are produced effectively
are embedded into it in such a manner as to
give the most stable electrostatic arrangement when electrons strike the dense metal anode,
(Fig. 2.4). Many different names are given called targets. These are not deflected by the
to this model, for example, plum pudding, electric and magnetic fields and have a very
raisin pudding or watermelon. This model high penetrating power through the matter
and that is the reason that these rays are
used to study the interior of the objects.
These rays are of very short wavelengths
(∼0.1 nm) and possess electro-magnetic
character (Section 2.3.1).
Henri Becqueral (1852-1908) observed
that there are certain elements which emit
radiation on their own and named this
Fig.2.4 Thomson model of atom phenomenon as radioactivity and the
can be visualised as a pudding or watermelon elements known as radioactive elements.
of positive charge with plums or seeds This field was developed by Marie Curie,
(electrons) embedded into it. An important Piere Curie, Rutherford and Fredrick Soddy.
feature of this model is that the mass of the It was observed that three kinds of rays i.e.,
atom is assumed to be uniformly distributed α, β- and γ-rays are emitted. Rutherford
over the atom. Although this model was able found that α-rays consists of high energy
to explain the overall neutrality of the atom, particles carrying two units of positive charge
but was not consistent with the results of later and four unit of atomic mass. He concluded
experiments. Thomson was awarded Nobel that α- particles are helium nuclei as when α-
Prize for physics in 1906, for his theoretical particles combined with two electrons yielded
and experimental investigations on the helium gas. β-rays are negatively charged
conduction of electricity by gases.

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 34 chemistry

represented in Fig. 2.5. A stream of high

particles similar to electrons. The γ-rays energy α–particles from a radioactive source
are high energy radiations like X-rays, are was directed at a thin foil (thickness ∼ 100 nm)
neutral in nature and do not consist of of gold metal. The thin gold foil had a circular
particles. As regards penetrating power, fluorescent zinc sulphide screen around it.
α-particles are the least, followed by β-rays Whenever α–particles struck the screen, a
(100 times that of α–particles) and γ-rays tiny flash of light was produced at that point.
(1000 times of that α-particles).
The results of scattering experiment were
quite unexpected. According to Thomson
2.2.2 Rutherford’s Nuclear Model of Atom model of atom, the mass of each gold atom
in the foil should have been spread evenly
Rutherford and his students (Hans Geiger over the entire atom, and α–particles had
and Ernest Marsden) bombarded very thin enough energy to pass directly through such a
gold foil with α–particles. Rutherford’s famous
uniform distribution of mass. It was expected
–particle scattering experiment is
that the particles would slow down and
change directions only by a small angles as
they passed through the foil. It was observed
that:
(i) most of the α–particles passed through
the gold foil undeflected.
(ii) a small fraction of the α–particles was
deflected by small angles.
(iii) a very few α–particles (∼1 in 20,000)
bounced back, that is, were deflected by
A. Rutherford’s scattering experiment nearly 180°.
On the basis of the observations,
Rutherford drew the following conclusions
regarding the structure of atom:
(i) Most of the space in the atom is empty as
most of the α–particles passed through
the foil undeflected.
(ii) A few positively charged α–particles were
deflected. The deflection must be due
to enormous repulsive force showing
that the positive charge of the atom
is not spread throughout the atom as
Thomson had presumed. The positive
charge has to be concentrated in a very
small volume that repelled and deflected
the positively charged α–particles.
B. Schematic molecular view of the gold foil
(iii) Calculations by Rutherford showed that
the volume occupied by the nucleus
Fig. 2.5 Schematic view of Rutherford’s
scattering experiment. When a beam
is negligibly small as compared to the
of alpha () particles is “shot” at a thin total volume of the atom. The radius of
gold foil, most of them pass through the atom is about 10–10 m, while that of
without much effect. Some, however, nucleus is 10–15 m. One can appreciate
are deflected. this difference in size by realising that if

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 structure of atom 35

a cricket ball represents a nucleus, then The total number of nucleons is termed as
the radius of atom would be about 5 km. mass number (A) of the atom.
On the basis of above observations and mass number (A) = number of protons (Z )
conclusions, Rutherford proposed the nuclear + number of
model of atom. According to this model: neutrons (n) (2.4)
(i) The positive charge and most of the mass 2.2.4 Isobars and Isotopes
of the atom was densely concentrated in The composition of any atom can be
extremely small region. This very small represented by using the normal element
portion of the atom was called nucleus symbol (X) with super-script on the left hand
by Rutherford. side as the atomic mass number (A) and
(ii) The nucleus is surrounded by electrons subscript (Z ) on the left hand side as the
that move around the nucleus with a atomic number (i.e., AZ X).
very high speed in circular paths called
orbits. Thus, Rutherford’s model of atom Isobars are the atoms with same mass
resembles the solar system in which the number but different atomic number for
nucleus plays the role of sun and the example, 146
C and 14 7
N. On the other hand,
electrons that of revolving planets. atoms with identical atomic number but
different atomic mass number are known
(iii) Electrons and the nucleus are held
as Isotopes. In other words (according to
together by electrostatic forces of
equation 2.4), it is evident that difference
attraction.
between the isotopes is due to the presence
2.2.3 Atomic Number and Mass Number of different number of neutrons present in
The presence of positive charge on the nucleus the nucleus. For example, considering of
is due to the protons in the nucleus. As hydrogen atom again, 99.985% of hydrogen
established earlier, the charge on the proton atoms contain only one proton. This isotope is
is equal but opposite to that of electron. The called protium (11H). Rest of the percentage of
number of protons present in the nucleus is hydrogen atom contains two other isotopes,
equal to atomic number (Z ). For example, the the one containing 1 proton and 1 neutron
number of protons in the hydrogen nucleus is called deuterium (12D, 0.015%) and the
is 1, in sodium atom it is 11, therefore their other one possessing 1 proton and 2 neutrons
atomic numbers are 1 and 11 respectively. is called tritium (13T ). The latter isotope is
In order to keep the electrical neutrality, found in trace amounts on the earth. Other
the number of electrons in an atom is equal examples of commonly occuring isotopes are:
to the number of protons (atomic number, carbon atoms containing 6, 7 and 8 neutrons
Z ). For example, number of electrons in besides 6 protons ( 12 13 14
); chlorine
6 C, 6 C, 6 C
hydrogen atom and sodium atom are 1 and
atoms containing 18 and 20 neutrons besides
11 respectively.
17 protons ( 17
35 37
Cl, 17 Cl ).
Atomic number (Z) = number of protons in
Lastly an important point to mention
the nucleus of an atom
regarding isotopes is that chemical properties
= number of electrons
of atoms are controlled by the number of
in a nuetral atom (2.3) electrons, which are determined by the number
While the positive charge of the nucleus of protons in the nucleus. Number of neutrons
is due to protons, the mass of the nucleus, present in the nucleus have very little effect
due to protons and neutrons. As discussed on the chemical properties of an element.
earlier protons and neutrons present in the Therefore, all the isotopes of a given element
nucleus are collectively known as nucleons. show same chemical behaviour.

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of the massive sun and the electrons being

Problem 2.1
similar to the lighter planets. When classical
Calculate the number of protons, mechanics* is applied to the solar system, it
neutrons and electrons in 80
35 Br
. shows that the planets describe well-defined
Solution orbits around the sun. The gravitational force
between the planets is given by the expression
In this case, 80
35 Br
, Z = 35, A = 80, species
 m1m 2 
is neutral  G. 2  where m1 and m2 are the masses,
r
Number of protons = number of electrons
= Z = 35 r is the distance of separation of the masses
and G is the gravitational constant. The theory
Number of neutrons = 80 – 35 = 45,
can also calculate precisely the planetary
(equation 2.4)
orbits and these are in agreement with the
Problem 2.2 experimental measurements.
The number of electrons, protons and The similarity between the solar system
neutrons in a species are equal to 18, 16 and nuclear model suggests that electrons
and 16 respectively. Assign the proper should move around the nucleus in well
symbol to the species.
defined orbits. Further, the coulomb force
Solution (kq1q2/r2 where q1 and q2 are the charges, r
is the distance of separation of the charges
The atomic number is equal to
and k is the proportionality constant) between
number of protons = 16. The element is
sulphur (S). electron and the nucleus is mathematically
similar to the gravitational force. However,
Atomic mass number = number of
when a body is moving in an orbit, it
protons + number of neutrons
undergoes acceleration even if it is moving
= 16 + 16 = 32 with a constant speed in an orbit because
Species is not neutral as the number of of changing direction. So an electron in the
protons is not equal to electrons. It is nuclear model describing planet like orbits
anion (negatively charged) with charge is under acceleration. According to the
equal to excess electrons = 18 – 16 = 2.
electromagnetic theory of Maxwell, charged
Symbol is .
A
particles when accelerated should emit
Note : Before using the notation Z X, electromagnetic radiation (This feature does
find out whether the species is a neutral not exist for planets since they are uncharged).
atom, a cation or an anion. If it is a Therefore, an electron in an orbit will emit
neutral atom, equation (2.3) is valid, i.e.,
radiation, the energy carried by radiation
number of protons = number of electrons
comes from electronic motion. The orbit will
= atomic number. If the species is an
ion, determine whether the number of thus continue to shrink. Calculations show
protons are larger (cation, positive ion) that it should take an electron only 10–8 s
or smaller (anion, negative ion) than the to spiral into the nucleus. But this does
number of electrons. Number of neutrons not happen. Thus, the Rutherford model
is always given by A–Z, whether the cannot explain the stability of an atom.
species is neutral or ion. If the motion of an electron is described on
the basis of the classical mechanics and
2.2.5 Drawbacks of Rutherford Model electromagnetic theory, you may ask that
As you have learnt above, Rutherford nuclear since the motion of electrons in orbits is
model of an atom is like a small scale solar leading to the instability of the atom, then
system with the nucleus playing the role why not consider electrons as stationary

* Classical mechanics is a theoretical science based on Newton’s laws of motion. It specifies the laws of motion of macroscopic
objects.

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 structure of atom 37

around the nucleus. If the electrons were was developed in the early 1870’s by James
stationary, electrostatic attraction between Clerk Maxwell, which was experimentally
the dense nucleus and the electrons would confirmed later by Heinrich Hertz. Here, we
pull the electrons toward the nucleus to will learn some facts about electromagnetic
form a miniature version of Thomson’s model radiations.
of atom.
James Maxwell (1870) was the first to
Another serious drawback of the give a comprehensive explanation about the
Rutherford model is that it says nothing interaction between the charged bodies and
about distribution of the electrons around the the behaviour of electrical and magnetic
nucleus and the energies of these electrons. fields on macroscopic level. He suggested
2.3 Developments Leading to the that when electrically charged particle moves
Bohr’s Model of Atom under accelaration, alternating electrical and
magnetic fields are produced and transmitted.
Historically, results observed from the studies
These fields are transmitted in the forms
of interactions of radiations with matter have
of waves called electromagnetic waves or
provided immense information regarding
electromagnetic radiation.
the structure of atoms and molecules. Neils
Bohr utilised these results to improve upon Light is the form of radiation known from
the model proposed by Rutherford. Two early days and speculation about its nature
developments played a major role in the dates back to remote ancient times. In earlier
formulation of Bohr’s model of atom. These days (Newton) light was supposed to be made
were: of particles (corpuscules). It was only in the
19th century when wave nature of light was
(i) Dual character of the electromagnetic
established.
radiation which means that radiations
possess both wave like and particle like Maxwell was again the first to reveal that
properties, and light waves are associated with oscillating
electric and magnetic character (Fig. 2.6).
(ii) Experimental results regarding atomic
spectra.
First, we will discuss about the duel nature
of electromagnetic radiations. Experimental
results regarding atomic spectra will be
discussed in Section 2.4.
2.3.1 Wave Nature of Electromagnetic
Radiation
In the mid-nineteenth century, physicists
actively studied absorption and emission of
radiation by heated objects. These are called
Fig.2.6 The electric and magnetic field
thermal radiations. They tried to find out of components of an electromagnetic
what the thermal radiation is made. It is now wave. These components have the
a well-known fact that thermal radiations same wavelength, frequency, speed
consist of electromagnetic waves of various and amplitude, but they vibrate in two
frequencies or wavelengths. It is based on mutually perpendicular planes.
a number of modern concepts, which were
unknown in the mid-nineteenth century. Although electromagnetic wave motion is
First active study of thermal radiation laws complex in nature, we will consider here only
occured in the 1850’s and the theory of a few simple properties.
electromagnetic waves and the emission of (i) The oscillating electric and magnetic
such waves by accelerating charged particles fields produced by oscillating charged

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 38 chemistry

particles are perpendicular to each (iv) Different kinds of units are used to
other and both are perpendicular to the represent electromagnetic radiation.
direction of propagation of the wave.
Simplified picture of electromagnetic These radiations are characterised by
wave is shown in Fig. 2.6. the properties, namely, frequency (ν ) and
(ii) Unlike sound waves or waves produced wavelength (λ).
in water, electromagnetic waves do The SI unit for frequency (ν) is hertz
not require medium and can move in (Hz, s–1), after Heinrich Hertz. It is defined as
vacuum. the number of waves that pass a given point
(iii) It is now well established that there in one second.
are many types of electromagnetic
radiations, which differ from one Wavelength should have the units of
another in wavelength (or frequency). length and as you know that the SI units of
These constitute what is called length is meter (m). Since electromagnetic
electromagnetic spectrum (Fig. 2.7). radiation consists of different kinds of waves
Different regions of the spectrum are of much smaller wavelengths, smaller units
identified by different names. Some are used. Fig. 2.7 shows various types of
examples are: radio frequency region electro-magnetic radiations which differ from
around 106 Hz, used for broadcasting;
one another in wavelengths and frequencies.
microwave region around 1010 Hz used
for radar; infrared region around 1013 In vaccum all types of electromagnetic
Hz used for heating; ultraviolet region radiations, regardless of wavelength, travel at
around 1016Hz a component of sun’s the same speed, i.e., 3.0 × 108 m s–1 (2.997925
radiation. The small portion around 1015 × 108 ms–1, to be precise). This is called speed
Hz, is what is ordinarily called visible of light and is given the symbol ‘c’. The
light. It is only this part which our eyes
frequency (ν ), wavelength (λ) and velocity of
can see (or detect). Special instruments
are required to detect non-visible light (c) are related by the equation (2.5).
radiation. c = ν λ (2.5)

(a)

(b)

Fig. 2.7 (a) The spectrum of electromagnetic radiation. (b) Visible spectrum. The visible region is only
a small part of the entire spectrum.

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 structure of atom 39

The other commonly used quantity Frequency of red light

specially in spectroscopy, is the wavenumber
( ). It is defined as the number of wavelengths
per unit length. Its units are reciprocal of ν= = 4.00 × 1014 Hz
wavelength unit, i.e., m–1. However commonly
The range of visible spectrum is from
used unit is cm–1 (not SI unit). 4.0 × 1014 to 7.5 × 1014 Hz in terms of
Problem 2.3 frequency units.
The Vividh Bharati station of All India Problem 2.5
Radio, Delhi, broadcasts on a frequency Calculate (a) wavenumber and (b)
of 1,368 kHz (kilo hertz). Calculate frequency of yellow radiation having
the wavelength of the electromagnetic wavelength 5800 Å.
radiation emitted by transmitter. Which
part of the electromagnetic spectrum Solution
does it belong to? (a) Calculation of wavenumber ( )
Solution λ=5800Å = 5800 × 10–8 cm
= 5800 × 10–10 m
The wavelength, λ, is equal to c/ν, where
c is the speed of electromagnetic radiation
in vacuum and ν is the frequency.
Substituting the given values, we have
c

v
(b) Calculation of the frequency (ν )

2.3.2 Particle Nature of Electromagnetic

Radiation: Planck’s Quantum
This is a characteristic radiowave Theory
wavelength. Some of the experimental phenomenon
such as diffraction* and interference** can
Problem 2.4
be explained by the wave nature of the
The wavelength range of the visible electromagnetic radiation. However, following
spectrum extends from violet (400 nm) to are some of the observations which could
red (750 nm). Express these wavelengths not be explained with the help of even the
in frequencies (Hz). (1nm = 10–9 m) electromagentic theory of 19th century
Solution physics (known as classical physics):
Using equation 2.5, frequency of violet (i) the nature of emission of radiation from
light hot bodies (black-body radiation)
(ii) ejection of electrons from metal surface
when radiation strikes it (photoelectric
effect)
= 7.50 × 1014 Hz
(iii) variation of heat capacity of solids as a
function of temperature

* Diffraction is the bending of wave around an obstacle.

** Interference is the combination of two waves of the same or different frequencies to give a wave whose distribution at each
point in space is the algebraic or vector sum of disturbances at that point resulting from each interfering wave.

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 40 chemistry

(iv) Line spectra of atoms with special entering the hole will be reflected by the cavity
reference to hydrogen. walls and will be eventually absorbed by the
These phenomena indicate that the system walls. A black body is also a perfect radiator of
can take energy only in discrete amounts. radiant energy. Furthermore, a black body is
All possible energies cannot be taken up or in thermal equilibrium with its surroundings.
radiated. It radiates same amount of energy per unit
area as it absorbs from its surrounding in
It is noteworthy that the first concrete
any given time. The amount of light emitted
explanation for the phenomenon of the black
(intensity of radiation) from a black body
body radiation mentioned above was given
and its spectral distribution depends only
by Max Planck in 1900. Let us first try to
on its temperature. At a given temperature,
understand this phenomenon, which is given
intensity of radiation emitted increases
below: with the increase of wavelength, reaches a
Ho t o b j e c t s e m i t e l e c t r o m a g n e t i c maximum value at a given wavelength and
radiations over a wide range of wavelengths. then starts decreasing with further increase of
At high temperatures, an appreciable wavelength, as shown in Fig. 2.8. Also, as the
proportion of radiation is in the visible temperature increases, maxima of the curve
region of the spectrum. As the temperature shifts to short wavelength. Several attempts
is raised, a higher proportion of short were made to predict the intensity of radiation
wavelength (blue light) is generated. For as a function of wavelength.
example, when an iron rod is heated in a But the results of the above experiment
furnace, it first turns to dull red and then could not be explained satisfactorily on
progressively becomes more and more red the basis of the wave theory of light. Max
as the temperature increases. As this is Planck arrived at a satisfactory relationship
heated further, the radiation emitted becomes
white and then becomes blue as the
temperature becomes very high. This means
that red radiation is most intense at a
particular temperature and the blue radiation
is more intense at another temperature. This
means intensities of radiations of different
wavelengths emitted by hot body depend
upon its temperature. By late 1850’s it was
known that objects made of different material
and kept at different temperatures emit
different amount of radiation. Also, when the
surface of an object is irradiated with light
(electromagnetic radiation), a part of radiant
energy is generally reflected as such, a part Fig. 2.8 Wavelength-intensity relationship
is absorbed and a part of it is transmitted.
The reason for incomplete absorption is
that ordinary objects are as a rule imperfect
absorbers of radiation. An ideal body, which
emits and absorbs radiations of all frequencies
uniformly, is called a black body and the
radiation emitted by such a body is called
black body radiation. In practice, no such
body exists. Carbon black approximates
fairly closely to black body. A good physical
approximation to a black body is a cavity with a
tiny hole, which has no other opening. Any ray Fig. 2.8(a) Black body

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 structure of atom 41

by making an assumption that absorption

and emmission of radiation arises from Max Planck
(1858–1947)
oscillator i.e., atoms in the wall of black
Max Planck, a German physicist,
body. Their frequency of oscillation is
received his Ph.D in theoretical
changed by interaction with oscilators of
physics from the University of
electromagnetic radiation. Planck assumed
Munich in 1879. In 1888, he
that radiation could be sub-divided into was appointed Director of the
discrete chunks of energy. He suggested that Institute of Theoretical Physics
atoms and molecules could emit or absorb at the University of Berlin.
energy only in discrete quantities and not Planck was awarded the Nobel Prize in Physics
in a continuous manner. He gave the name in 1918 for his quantum theory. Planck also made
quantum to the smallest quantity of energy significant contributions in thermodynamics and
that can be emitted or absorbed in the form other areas of physics.
of electromagnetic radiation. The energy (E)
of a quantum of radiation is proportional Photoelectric Effect
to its frequency (ν) and is expressed by In 1887, H. Hertz performed a very interesting
equation (2.6). experiment in which electrons (or electric
E = hυ (2.6) current) were ejected when certain metals
The proportionality constant, ‘h’ is known (for example potassium, rubidium, caesium
as Planck’s constant and has the value etc.) were exposed to a beam of light as shown
6.626×10–34 J s. in Fig. 2.9. The phenomenon is called
Photoelectric effect. The results observed
With this theory, Planck was able to explain in this experiment were:
the distribution of intensity in the radiation
from black body as a function of frequency or (i) The electrons are ejected from the metal
wavelength at different temperatures. surface as soon as the beam of light
strikes the surface, i.e., there is no time
Quantisation has been compared to
lag between the striking of light beam and
standing on a staircase. A person can stand
the ejection of electrons from the metal
on any step of a staircase, but it is not possible
surface.
for him/her to stand in between the two steps.
The energy can take any one of the values (ii) The number of electrons ejected is
from the following set, but cannot take on any proportional to the intensity or brightness
values between them. of light.
E = 0, hυ, 2hυ , 3hυ....nhυ..... (iii) For each metal, there is a characteristic
minimum frequency, ν 0 (also known
as threshold frequency) below which
photoelectric effect is not observed. At
a frequency ν >ν0, the ejected electrons
come out with certain kinetic energy.
The kinetic energies of these electrons
increase with the increase of frequency
of the light used.
All the above results could not be explained
on the basis of laws of classical physics.
Fig.2.9 Equipment for studying the photoelectric According to latter, the energy content of the
effect. Light of a particular frequency beam of light depends upon the brightness of
strikes a clean metal surface inside a the light. In other words, number of electrons
vacuum chamber. Electrons are ejected
from the metal and are counted by a
ejected and kinetic energy associated with
detector that measures their kinetic them should depend on the brightness of light.
energy. It has been observed that though the number

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 42 chemistry

Table 2.2 Values of Work Function (W0) for a Few Metals

Metal Li Na K Mg Cu Ag

W0 /eV 2.42 2.3 2.25 3.7 4.8 4.3

of electrons ejected does depend upon the the minimum energy required to eject the
brightness of light, the kinetic energy of the electron is hν0 (also called work function,
ejected electrons does not. For example, red W0 ; Table 2.2), then the difference in energy
light [ν = (4.3 to 4.6) × 1014 Hz] of any brightness (hν – hν0 ) is transferred as the kinetic energy of
(intensity) may shine on a piece of potassium the photoelectron. Following the conservation
metal for hours but no photoelectrons are of energy principle, the kinetic energy of the
ejected. But, as soon as even a very weak ejected electron is given by the equation 2.7.
yellow light (ν = 5.1–5.2 × 1014 Hz) shines on
the potassium metal, the photoelectric effect (2.7)
is observed. The threshold frequency (ν0) for where me is the mass of the electron and v is the
potassium metal is 5.0×1014 Hz. velocity associated with the ejected electron.
Einstein (1905) was able to explain the Lastly, a more intense beam of light consists
photoelectric effect using Planck’s quantum of larger number of photons, consequently the
theory of electromagnetic radiation as a number of electrons ejected is also larger as
starting point. compared to that in an experiment in which a
beam of weaker intensity of light is employed.
Albert Einstein, a German born
American physicist, is regarded Dual Behaviour of Electromagnetic
by many as one of the two great Radiation
physicists the world has known
(the other is Isaac Newton). His The particle nature of light posed a dilemma for
three research papers (on special scientists. On the one hand, it could explain
relativity, Brownian motion and the black body radiation and photoelectric
the photoelectric effect) which Albert Einstein
effect satisfactorily but on the other hand,
he published in 1905, while he (1879–1955)
was employed as a technical it was not consistent with the known wave
assistant in a Swiss patent office in Berne have behaviour of light which could account for the
profoundly influenced the development of physics. phenomena of interference and diffraction.
He received the Nobel Prize in Physics in 1921 for The only way to resolve the dilemma was
his explanation of the photoelectric effect.
to accept the idea that light possesses
both particle and wave-like properties, i.e.,
Shining a beam of light on to a metal
surface can, therefore, be viewed as shooting light has dual behaviour. Depending on
a beam of particles, the photons. When a the experiment, we find that light behaves
photon of sufficient energy strikes an electron either as a wave or as a stream of particles.
in the atom of the metal, it transfers its energy Whenever radiation interacts with matter, it
instantaneously to the electron during the displays particle like properties in contrast
collision and the electron is ejected without to the wavelike properties (interference
any time lag or delay. Greater the energy and diffraction), which it exhibits when it
possessed by the photon, greater will be propagates. This concept was totally alien to
transfer of energy to the electron and greater the way the scientists thought about matter
the kinetic energy of the ejected electron. In and radiation and it took them a long time to
other words, kinetic energy of the ejected become convinced of its validity. It turns out,
electron is proportional to the frequency as you shall see later, that some microscopic
of the electromagnetic radiation. Since the particles like electrons also exhibit this wave-
striking photon has energy equal to hν and particle duality.

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 structure of atom 43

Problem 2.6 Solution

Calculate energy of one mole of photons The energy (E) of a 300 nm photon is
of radiation whose frequency is 5 ×1014 given by
Hz.
Solution
Energy (E) of one photon is given by the
expression = 6.626 × 10–19 J
E = hν The energy of one mole of photons
h = 6.626 ×10–34 J s
= 6.626 ×10–19 J × 6.022 × 1023 mol–1
ν = 5×1014 s–1 (given)
= 3.99 × 105 J mol–1
E = (6.626 ×10–34 J s) × (5 ×1014 s–1)
The minimum energy needed to remove
= 3.313 ×10–19 J one mole of electrons from sodium
Energy of one mole of photons = (3.99 –1.68) 105 J mol–1
= (3.313 ×10–19 J) × (6.022 × 1023 mol–1) = 2.31 × 105 J mol–1
= 199.51 kJ mol–1 The minimum energy for one electron

Problem 2.7
A 100 watt bulb emits monochromatic
light of wavelength 400 nm. Calculate the
number of photons emitted per second This corresponds to the wavelength
by the bulb. hc
=
Solution E
6.626 10 34 J s 3.0 108 m s 1

Power of the bulb = 100 watt =

3.84 10 19 J
= 100 J s–1
= 517 nm
Energy of one photon E = hν = hc/λ (This corresponds to green light)
6.626  10 34 J s  3  108 m s 1 Problem 2.9
=
400  10 9 m The threshold frequency ν0 for a metal is
= 4.969 × 10–19 J 7.0 ×1014 s–1. Calculate the kinetic energy
of an electron emitted when radiation of
Number of photons emitted frequency ν =1.0 ×1015 s–1 hits the metal.
100 J s 1 Solution
 2.012  1020 s 1
4.969  10 19 J According to Einstein’s equation
Problem 2.8 Kinetic energy = ½ mev2=h(ν – ν0 )
When electromagnetic radiation of = (6.626 × 10–34 J s) (1.0 × 1015 s–1 – 7.0
wavelength 300 nm falls on the surface ×1014 s–1)
of sodium, electrons are emitted with a = (6.626 × 10–34 J s) (10.0 × 1014 s–1 – 7.0
kinetic energy of 1.68 ×105 J mol–1. What ×1014 s–1)
is the minimum energy needed to remove
= (6.626 × 10–34 J s) × (3.0 × 1014 s–1)
an electron from sodium? What is the
maximum wavelength that will cause a = 1.988 × 10–19 J
photoelectron to be emitted?

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 44 chemistry

2.3.3 Evidence for the quantized* spectrum. A continuum of radiation is passed

Electronic Energy Levels: Atomic through a sample which absorbs radiation of
spectra certain wavelengths. The missing wavelength
The speed of light depends upon the nature which corresponds to the radiation absorbed
of the medium through which it passes. As a by the matter, leave dark spaces in the bright
result, the beam of light is deviated or refracted continuous spectrum.
from its original path as it passes from one The study of emission or absorption
medium to another. It is observed that when spectra is referred to as spectroscopy. The
a ray of white light is passed through a prism, spectrum of the visible light, as discussed
the wave with shorter wavelength bends more above, was continuous as all wavelengths (red
than the one with a longer wavelength. Since to violet) of the visible light are represented in
ordinary white light consists of waves with the spectra. The emission spectra of atoms in
all the wavelengths in the visible range, a ray the gas phase, on the other hand, do not show
of white light is spread out into a series of a continuous spread of wavelength from red
coloured bands called spectrum. The light of to violet, rather they emit light only at specific
red colour which has longest wavelength is wavelengths with dark spaces between them.
deviated the least while the violet light, which Such spectra are called line spectra or
has shortest wavelength is deviated the most. atomic spectra because the emitted radiation
The spectrum of white light, that we can is identified by the appearance of bright lines
see, ranges from violet at 7.50 × 1014 Hz to in the spectra (Fig. 2.10 page 45).
red at 4×1014 Hz. Such a spectrum is called Line emission spectra are of great
continuous spectrum. Continuous because interest in the study of electronic structure.
violet merges into blue, blue into green and Each element has a unique line emission
so on. A similar spectrum is produced when spectrum. The characteristic lines in atomic
a rainbow forms in the sky. Remember that spectra can be used in chemical analysis to
visible light is just a small portion of the identify unknown atoms in the same way
electromagnetic radiation (Fig.2.7). When as fingerprints are used to identify people.
electromagnetic radiation interacts with The exact matching of lines of the emission
matter, atoms and molecules may absorb spectrum of the atoms of a known element
energy and reach to a higher energy state. With with the lines from an unknown sample
higher energy, these are in an unstable state. quickly establishes the identity of the latter,
For returning to their normal (more stable, German chemist, Robert Bunsen (1811-1899)
lower energy states) energy state, the atoms was one of the first investigators to use line
and molecules emit radiations in various spectra to identify elements.
regions of the electromagnetic spectrum. Elements like rubidium (Rb), caesium (Cs)
thallium (Tl), indium (In), gallium (Ga) and
Emission and Absorption Spectra scandium (Sc) were discovered when their
The spectrum of radiation emitted by a minerals were analysed by spectroscopic
substance that has absorbed energy is called methods. The element helium (He) was
an emission spectrum. Atoms, molecules or discovered in the sun by spectroscopic method.
ions that have absorbed radiation are said Line Spectrum of Hydrogen
to be “excited”. To produce an emission When an electric discharge is passed through
spectrum, energy is supplied to a sample by gaseous hydrogen, the H2 molecules dissociate
heating it or irradiating it and the wavelength and the energetically excited hydrogen atoms
(or frequency) of the radiation emitted, as produced emit electromagnetic radiation of
the sample gives up the absorbed energy, is discrete frequencies. The hydrogen spectrum
recorded. consists of several series of lines named after
An absorption spectrum is like the their discoverers. Balmer showed in 1885
photographic negative of an emission on the basis of experimental observations
* The restriction of any property to discrete values is called quantization.

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 structure of atom 45

(a)

(b)

Fig. 2.10 (a) Atomic emission. The light emitted by a sample of excited hydrogen atoms (or any other
element) can be passed through a prism and separated into certain discrete wavelengths. Thus an emission
spectrum, which is a photographic recording of the separated wavelengths is called as line spectrum. Any
sample of reasonable size contains an enormous number of atoms. Although a single atom can be in only
one excited state at a time, the collection of atoms contains all possible excited states. The light emitted as
these atoms fall to lower energy states is responsible for the spectrum. (b) Atomic absorption. When white
light is passed through unexcited atomic hydrogen and then through a slit and prism, the transmitted light
is lacking in intensity at the same wavelengths as are emitted in (a) The recorded absorption spectrum is
also a line spectrum and the photographic negative of the emission spectrum.

that if spectral lines are expressed in terms The value 109,677 cm –1 is called the
of wavenumber ( ), then the visible lines of Rydberg constant for hydrogen. The first five
the hydrogen spectrum obey the following series of lines that correspond to n1 = 1, 2, 3,
formula: 4, 5 are known as Lyman, Balmer, Paschen,
Bracket and Pfund series, respectively,
(2.8) Table 2.3 shows these series of transitions in
where n is an integer equal to or greater than the hydrogen spectrum. Fig. 2.11 (page, 46)
3 (i.e., n = 3,4,5,....) shows the Lyman, Balmer and Paschen series
of transitions for hydrogen atom.
The series of lines described by this formula
Of all the elements, hydrogen atom has
are called the Balmer series. The Balmer
the simplest line spectrum. Line spectrum
series of lines are the only lines in the hydrogen
spectrum which appear in the visible region
of the electromagnetic spectrum. The Swedish Table 2.3 The Spectral Lines for Atomic
spectroscopist, Johannes Rydberg, noted Hydrogen
that all series of lines in the hydrogen
Series n1 n2 Spectral Region
spectrum could be described by the following
expression : Lyman 1 2,3.... Ultraviolet

(2.9) Balmer 2 3,4.... Visible

Paschen 3 4,5.... Infrared
where n1=1,2........ Brackett 4 5,6.... Infrared
n2 = n1 + 1, n1 + 2...... Pfund 5 6,7.... Infrared

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 46 chemistry

atomic structure and spectra. Bohr’s model

for hydrogen atom is based on the following
postulates:
i) The electron in the hydrogen atom can
move around the nucleus in a circular
path of fixed radius and energy. These
paths are called orbits, stationary states
or allowed energy states. These orbits
are arranged concentrically around the
nucleus.
ii) The energy of an electron in the orbit
does not change with time. However,
the electron will move from a lower
stationary state to a higher stationary
state when required amount of energy
is absorbed by the electron or energy is
emitted when electron moves from higher
stationary state to lower stationary state
(equation 2.16). The energy change does
not take place in a continuous manner.

Angular Momentum

Fig. 2.11 Transitions of the electron in the Just as linear momentum is the product
hydrogen atom (The diagram shows the of mass (m) and linear velocity (v), angular
Lyman, Balmer and Paschen series of momentum is the product of moment of
transitions) inertia (I) and angular velocity (ω). For an
electron of mass me, moving in a circular
becomes more and more complex for heavier path of radius r around the nucleus,
atom. There are, however, certain features angular momentum = I × ω
which are common to all line spectra, i.e.,
Since I = mer2, and ω = v/r where v is the
(i) line spectrum of element is unique and linear velocity,
(ii) there is regularity in the line spectrum of
∴angular momentum = mer2 × v/r = mevr
each element. The questions which arise are:
What are the reasons for these similarities?
Is it something to do with the electronic iii) The frequency of radiation absorbed or
emitted when transition occurs between
structure of atoms? These are the questions
two stationary states that differ in
need to be answered. We shall find later that
energy by ∆E, is given by:
the answers to these questions provide the
key in understanding electronic structure of (2.10)
these elements.
Where E1 and E2 are the energies of the
2.4 Bohr’s Model for Hydrogen
lower and higher allowed energy states
Atom
respectively. This expression is commonly
Neils Bohr (1913) was the first to explain known as Bohr’s frequency rule.
quantitatively the general features of the
iv) The angular momentum of an electron
structure of hydrogen atom and its spectrum.
is quantised. In a given stationary state
He used Planck’s concept of quantisation
it can be expressed as in equation (2.11)
of energy. Though the theory is not the
modern quantum mechanics, it can still h
m e v r  n. n = 1,2,3..... (2.11)
be used to rationalize many points in the 2

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 structure of atom 47

Where me is the mass of electron, v is the

velocity and r is the radius of the orbit in Niels Bohr
(1885–1962)
which electron is moving.
Niels Bohr, a Danish physicist
Thus an electron can move only in those received his Ph.D. from the
orbits for which its angular momentum is University of Copenhagen in
integral multiple of h/2π. That means angular 1911. He then spent a year
momentum is quantised. Radiation is emitted with J.J. Thomson and Ernest
or obsorbed only when transition of electron Rutherford in England. In 1913,
takes place from one quantised value of he returned to Copenhagen where he remained for
angular momentum to another. Therefore, the rest of his life. In 1920 he was named Director
Maxwell’s electromagnetic theory does not of the Institute of theoretical Physics. After first
World War, Bohr worked energetically for peaceful
apply here that is why only certain fixed orbits
uses of atomic energy. He received the first Atoms
are allowed.
for Peace award in 1957. Bohr was awarded the
The details regarding the derivation of Nobel Prize in Physics in 1922.
energies of the stationary states used by Bohr,
are quite complicated and will be discussed in
higher classes. However, according to Bohr’s Fig. 2.11 depicts the energies of different
theory for hydrogen atom: stationary states or energy levels of hydrogen
a) The stationary states for electron are atom. This representation is called an energy
numbered n = 1,2,3.......... These integral level diagram.
numbers (Section 2.6.2) are known as When the electron is free from the influence
Principal quantum numbers. of nucleus, the energy is taken as zero. The
b) The radii of the stationary states are electron in this situation is associated with the
expressed as: stationary state of Principal Quantum number
= n = ∞ and is called as ionized hydrogen atom.
rn = n2 a0 (2.12)
When the electron is attracted by the nucleus
where a0 = 52.9 pm. Thus the radius of and is present in orbit n, the energy is emitted
the first stationary state, called the Bohr and its energy is lowered. That is the reason
orbit, is 52.9 pm. Normally the electron
in the hydrogen atom is found in this
orbit (that is n=1). As n increases the What does the negative electronic
value of r will increase. In other words energy (En) for hydrogen atom mean?
the electron will be present away from The energy of the electron in a hydrogen
the nucleus. atom has a negative sign for all possible
c) The most important property associated orbits (eq. 2.13). What does this negative
sign convey? This negative sign means
with the electron, is the energy of its
that the energy of the electron in the
stationary state. It is given by the
atom is lower than the energy of a free
expression. electron at rest. A free electron at rest
 1 is an electron that is infinitely far away
En   R H  2  n = 1,2,3.... (2.13) from the nucleus and is assigned the
n 
energy value of zero. Mathematically, this
where RH is called Rydberg constant and
corresponds to setting n equal to infinity
its value is 2.18×10–18 J. The energy of the
in the equation (2.13) so that E∞=0. As the
lowest state, also called as the ground state, is electron gets closer to the nucleus (as n
1 decreases), En becomes larger in absolute
E1 = –2.18×10–18 ( 2 ) = –2.18×10–18 J. The
1 value and more and more negative. The
energy of the stationary state for n = 2, will most negative energy value is given by
n=1 which corresponds to the most stable
1
be : E2 = –2.18×10–18J ( 2 ) = –0.545×10–18 J. orbit. We call this the ground state.
2

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 48 chemistry

for the presence of negative sign in equation

 R   R 
(2.13) and depicts its stability relative to the  E    2H     2H  (where n and n
reference state of zero energy and n = ∞.  nf   ni  i f

d) Bohr’s theory can also be applied to stand for initial orbit and final orbits)
the ions containing only one electron,  1 1  1 1
18
similar to that present in hydrogen ∆E  R H  2  2   2.18  10 J  2  2 
atom. For example, He+ Li2+, Be3+ and so  ni nf   ni nf 
on. The energies of the stationary states
associated with these kinds of ions (also (2.17)
known as hydrogen like species) are The frequency (ν) associated with the
given by the expression. absorption and emission of the photon can
 Z2 be evaluated by using equation (2.18)
E n   2.18  10 18  2  J (2.14)
n 
and radii by the expression
52.9 (n 2 ) (2.15)
rn = pm 2.18  10 18 J  1 1 (2.18)
Z  34   2
6.626  10 J s  n i n f 
2
where Z is the atomic number and has
values 2,3 for the helium and lithium atoms
 1 1
respectively. From the above equations, it is  3.29  1015  2  2  Hz (2.19)
evident that the value of energy becomes more  ni nf 
negative and that of radius becomes smaller
and in terms of wavenumbers ( )
with increase of Z. This means that electron
will be tightly bound to the nucleus.
(2.20)
e) It is also possible to calculate the
velocities of electrons moving in these
orbits. Although the precise equation 3.29  1015 s 1  1 1
is not given here, qualitatively the = 
3  108 m s  s  n i2 n f2 
magnitude of velocity of electron
increases with increase of positive  1 1
charge on the nucleus and decreases = 1.09677  107  2  2  m 1 (2.21)
with increase of principal quantum  ni nf 
number. In case of absorption spectrum, nf > ni and
the term in the parenthesis is positive and
2.4.1 Explanation of Line Spectrum of energy is absorbed. On the other hand in case
Hydrogen of emission spectrum ni > nf , ∆ E is negative
Line spectrum observed in case of hydrogen and energy is released.
atom, as mentioned in section 2.3.3, can be The expression (2.17) is similar to that
explained quantitatively using Bohr’s model. used by Rydberg (2.9) derived empirically
According to assumption 2, radiation (energy) using the experimental data available at that
is absorbed if the electron moves from the time. Further, each spectral line, whether
orbit of smaller Principal quantum number to in absorption or emission spectrum, can
the orbit of higher Principal quantum number, be associated to the particular transition in
whereas the radiation (energy) is emitted if hydrogen atom. In case of large number of
the electron moves from higher orbit to lower hydrogen atoms, different possible transitions
orbit. The energy gap between the two orbits can be observed and thus leading to large
is given by equation (2.16) number of spectral lines. The brightness or
∆E = Ef – Ei (2.16) intensity of spectral lines depends upon the
number of photons of same wavelength or
Combining equations (2.13) and (2.16)
frequency absorbed or emitted.

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 structure of atom 49

2.4.2 Limitations of Bohr’s Model

Problem 2.10
Bohr’s model of the hydrogen atom was no
What are the frequency and wavelength doubt an improvement over Rutherford’s
of a photon emitted during a transition nuclear model, as it could account for the
from n = 5 state to the n = 2 state in the stability and line spectra of hydrogen atom
hydrogen atom? and hydrogen like ions (for example, He+, Li2+,
Solution Be3+, and so on). However, Bohr’s model was
too simple to account for the following points.
Since ni = 5 and nf = 2, this transition
gives rise to a spectral line in the visible i) It fails to account for the finer details
region of the Balmer series. From (doublet, that is two closely spaced lines)
equation (2.17) of the hydrogen atom spectrum observed
by using sophisticated spectroscopic
1 1 techniques. This model is also unable
E = 2.18  10 18 J  2  2  to explain the spectrum of atoms
5 2 
19 other than hydrogen, for example,
=  4.58  10 J helium atom which possesses only two
It is an emission energy electrons. Further, Bohr’s theory was
The frequency of the photon (taking also unable to explain the splitting
energy in terms of magnitude) is given by of spectral lines in the presence of
magnetic field (Zeeman effect) or an
electric field (Stark effect).
ii) It could not explain the ability of atoms
to form molecules by chemical bonds.
In other words, taking into account the
points mentioned above, one needs a better
= 6.91×1014 Hz theory which can explain the salient features
of the structure of complex atoms.
2.5 Towards Quantum Mechanical
Problem 2.11 Model of the Atom
Calculate the energy associated with the In view of the shortcoming of the Bohr’s
first orbit of He+. What is the radius of model, attempts were made to develop a more
this orbit? suitable and general model for atoms. Two
important developments which contributed
Solution significantly in the formulation of such a
(2.18  10 18 J)Z 2 model were:
En   atom–1
n2 1. Dual behaviour of matter,
For He+, n = 1, Z = 2 2. Heisenberg uncertainty principle.
(2.18  10 18 J)(22 )
E1    8.72  10 18 J 2.5.1 Dual Behaviour of Matter
12
The French physicist, de Broglie, in 1924
The radius of the orbit is given by proposed that matter, like radiation, should
equation (2.15) also exhibit dual behaviour i.e., both particle
(0.0529 nm )n 2 and wavelike properties. This means that
rn = just as the photon has momentum as well
Z
as wavelength, electrons should also have
Since n = 1, and Z = 2
momentum as well as wavelength, de Broglie,
(0.0529 nm )12 from this analogy, gave the following relation
=rn = 0.02645 nm between wavelength (λ) and momentum (p) of
2
a material particle.

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 50 chemistry

Louis de Broglie Solution

(1892 – 1987)
Louis de Broglie, a French According to de Brogile equation (2.22)
physicist, studied history
as an undergraduate in the h (6.626  10 34 Js)
 
early 1910’s. His interest mv (0.1 kg )(10 m s 1 )
turned to science as a result
of his assignment to radio = 6.626 × 10–34 m (J = kg m2 s–2)
communications in World
Problem 2.13
War I. He received his
Dr. Sc. from the University of Paris in 1924. The mass of an electron is 9.1×10–31 kg.
He was professor of theoretical physics at If its K.E. is 3.0×10–25 J, calculate its
the University of Paris from 1932 untill his wavelength.
retirement in 1962. He was awarded the
Solution
Nobel Prize in Physics in 1929.
Since K.E. = ½ mv2
1/ 2 1/ 2
h h  2K.E.  2  3.0  10 25 kg m 2 s 2 
  (2.22) v = =
mv p  m   9.1  10 31 kg 
where m is the mass of the particle, v its
= 812 m s–1
velocity and p its momentum. de Broglie’s 34
prediction was confirmed experimentally when h 6 .626 10 Js
it was found that an electron beam undergoes m v ( 9. 1 10
31
kg )(812 m s )
1

diffraction, a phenomenon characteristic of

waves. This fact has been put to use in making = 8967 × 10–10 m = 896.7 nm
an electron microscope, which is based on Problem 2.14
the wavelike behaviour of electrons just as an
ordinary microscope utilises the wave nature Calculate the mass of a photon with
of light. An electron microscope is a powerful wavelength 3.6 Å.
tool in modern scientific research because it Solution
achieves a magnification of about 15 million λ = 3.6 Å = 3.6 × 10–10 m
times. Velocity of photon = velocity of light
It needs to be noted that according to de 34
Broglie, every object in motion has a wave
10 8
character. The wavelengths associated with 1

ordinary objects are so short (because of their

large masses) that their wave properties cannot = 6.135 × 10–29 kg
be detected. The wavelengths associated with
electrons and other subatomic particles (with
very small mass) can however be detected 2.5.2 Heisenberg’s Uncertainty Principle
experimentally. Results obtained from Werner Heisenberg a German physicist in
the following problems prove these points 1927, stated uncertainty principle which is
qualitatively. the consequence of dual behaviour of matter
and radiation. It states that it is impossible
to determine simultaneously, the exact
Problem 2.12 position and exact momentum (or velocity)
What will be the wavelength of a ball of of an electron.
mass 0.1 kg moving with a velocity of
Mathematically, it can be given as in
10 m s–1 ?
equation (2.23).

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 structure of atom 51

(2.23)  h
momentum photons of such light  p = 
 
would change the energy of electrons by
collisions. In this process we, no doubt,
would be able to calculate the position of the
electron, but we would know very little about
where ∆x is the uncertainty in position and the velocity of the electron after the collision.
∆px (or ∆vx ) is the uncertainty in momentum Significance of Uncertainty Principle
(or velocity) of the particle. If the position of
One of the important implications of the
the electron is known with high degree of
Heisenberg Uncertainty Principle is that it
accuracy (∆x is small), then the velocity of the
rules out existence of definite paths or
electron will be uncertain [∆(vx) is large]. On
trajectories of electrons and other similar
the other hand, if the velocity of the electron particles. The trajectory of an object is
is known precisely (∆(vx ) is small), then the determined by its location and velocity at
position of the electron will be uncertain various moments. If we know where a body
(∆x will be large). Thus, if we carry out some is at a particular instant and if we also know
physical measurements on the electron’s its velocity and the forces acting on it at that
position or velocity, the outcome will always instant, we can tell where the body would
depict a fuzzy or blur picture. be sometime later. We, therefore, conclude
The uncertainty principle can be best that the position of an object and its velocity
fix its trajectory. Since for a sub-atomic
understood with the help of an example.
object such as an electron, it is not possible
Suppose you are asked to measure the
simultaneously to determine the position and
thickness of a sheet of paper with an
velocity at any given instant to an arbitrary
unmarked metrestick. Obviously, the results degree of precision, it is not possible to talk
obtained would be extremely inaccurate of the trajectory of an electron.
and meaningless. In order to obtain any
accuracy, you should use an instrument The effect of Heisenberg Uncertainty
graduated in units smaller than the thickness Principle is significant only for motion of
microscopic objects and is negligible for
of a sheet of the paper. Analogously, in order
that of macroscopic objects. This can be
to determine the position of an electron, we
seen from the following examples.
must use a meterstick calibrated in units of
smaller than the dimensions of electron (keep If uncertainty principle is applied to an
object of mass, say about a milligram (10–6 kg),
in mind that an electron is considered as a
then
point charge and is therefore, dimensionless).
To observe an electron, we can illuminate it
with “light” or electromagnetic radiation. The
“light” used must have a wavelength smaller
than the dimensions of an electron. The high

Werner Heisenberg (1901 – 1976) Werner Heisenberg (1901 – 1976) received his Ph.D. in
physics from the University of Munich in 1923. He then spent a year working with Max
Born at Gottingen and three years with Niels Bohr in Copenhagen. He was professor of
physics at the University of Leipzig from 1927 to 1941. During World War II, Heisenberg
was in charge of German research on the atomic bomb. After the war he was named
director of Max Planck Institute for physics in Gottingen. He was also accomplished
mountain climber. Heisenberg was awarded the Nobel Prize in Physics in 1932.

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The value of ∆v∆x obtained is extremely

small and is insignificant. Therefore, one
may say that in dealing with milligram-
sized or heavier objects, the associated
uncertainties are hardly of any real
consequence.
In the case of a microscopic object like an = 0.579×107 m s–1 (1J = 1 kg m2 s–2)
electron on the other hand. ∆v.∆x obtained is = 5.79×106 m s–1
much larger and such uncertainties are of real
consequence. For example, for an electron Problem 2.16
whose mass is 9.11×10–31 kg., according to A golf ball has a mass of 40g, and a speed
Heisenberg uncertainty principle of 45 m/s. If the speed can be measured
within accuracy of 2%, calculate the
uncertainty in the position.
Solution
The uncertainty in the speed is 2%, i.e.,

Using the equation (2.22)

It, therefore, means that if one tries to
find the exact location of the electron, say
to an uncertainty of only 10–8 m, then the
uncertainty ∆v in velocity would be
10 4 m 2 s 1
 104 ms 1 = 1.46×10–33 m
10 8 m
This is nearly ~ 10 18 times smaller
which is so large that the classical picture than the diameter of a typical atomic
of electrons moving in Bohr’s orbits (fixed) nucleus. As mentioned earlier for large
cannot hold good. It, therefore, means that particles, the uncertainty principle sets
the precise statements of the position no meaningful limit to the precision of
and momentum of electrons have to be measurements.
replaced by the statements of probability,
that the electron has at a given position
and momentum. This is what happens in Reasons for the Failure of the Bohr Model
the quantum mechanical model of atom. One can now understand the reasons for the
failure of the Bohr model. In Bohr model,
an electron is regarded as a charged particle
Problem 2.15 moving in well defined circular orbits about
A microscope using suitable photons is the nucleus. The wave character of the
employed to locate an electron in an atom electron is not considered in Bohr model.
within a distance of 0.1 Å. What is the Further, an orbit is a clearly defined path
uncertainty involved in the measurement and this path can completely be defined
of its velocity? only if both the position and the velocity of
the electron are known exactly at the same
Solution
time. This is not possible according to the
∆ x ∆p = or ∆ x m ∆ v Heisenberg uncertainty principle. Bohr model
of the hydrogen atom, therefore, not only
ignores dual behaviour of matter but also
contradicts Heisenberg uncertainty principle.

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 structure of atom 53

these objects obey. When quantum mechanics

Erwin Schrödinger, an is applied to macroscopic objects (for which
Austrian physicist received
wave like properties are insignificant) the
his Ph.D. in theoretical
results are the same as those from the
physics from the University
classical mechanics.
of Vienna in 1910. In 1927
Schrödinger succeeded Max Quantum mechanics was developed
Planck at the University of independently in 1926 by Werner Heisenberg
Berlin at Planck’s request. and Erwin Schrödinger. Here, however, we
In 1933, Schrödinger left shall be discussing the quantum mechanics
B e r l i n b e c a u s e o f h i s Erwin Schrödinger which is based on the ideas of wave motion.
opposition to Hitler and (1887–1961) The fundamental equation of quantum
Nazi policies and returned mechanics was developed by Schrödinger
to Austria in 1936. After the invasion of Austria and it won him the Nobel Prize in Physics in
by Germany, Schrödinger was forcibly removed 1933. This equation which incorporates wave-
from his professorship. He then moved to Dublin, particle duality of matter as proposed by de
Ireland where he remained for seventeen years.
Broglie is quite complex and knowledge of
Schrödinger shared the Nobel Prize for Physics
higher mathematics is needed to solve it. You
with P.A.M. Dirac in 1933.
will learn its solutions for different systems
in higher classes.
In view of these inherent weaknesses in the For a system (such as an atom or a
Bohr model, there was no point in extending molecule whose energy does not change with
Bohr model to other atoms. In fact an insight time) the Schrödinger equation is written
into the structure of the atom was needed as where is a mathematical
which could account for wave-particle duality operator called Hamiltonian. Schrödinger
of matter and be consistent with Heisenberg gave a recipe of constructing this operator
uncertainty principle. This came with the from the expression for the total energy of
advent of quantum mechanics. the system. The total energy of the system
takes into account the kinetic energies of all
2.6 Quantum Mechanical Model of the sub-atomic particles (electrons, nuclei),
Atom attractive potential between the electrons
Classical mechanics, based on Newton’s and nuclei and repulsive potential among the
laws of motion, successfully describes the electrons and nuclei individually. Solution of
motion of all macroscopic objects such as a this equation gives E and ψ.
falling stone, orbiting planets etc., which have
Hydrogen Atom and the Schrödinger
essentially a particle-like behaviour as shown
Equation
in the previous section. However it fails when
applied to microscopic objects like electrons, When Schrödinger equation is solved for
atoms, molecules etc. This is mainly because hydrogen atom, the solution gives the possible
of the fact that classical mechanics ignores energy levels the electron can occupy and
the concept of dual behaviour of matter the corresponding wave function(s) (ψ) of
especially for sub-atomic particles and the the electron associated with each energy
uncertainty principle. The branch of science level. These quantized energy states and
that takes into account this dual behaviour corresponding wave functions which are
characterized by a set of three quantum
of matter is called quantum mechanics.
numbers (principal quantum number
Quantum mechanics is a theoretical n, azimuthal quantum number l and
science that deals with the study of the magnetic quantum number m l ) arise as a
motions of the microscopic objects that have natural consequence in the solution of the
both observable wave like and particle like Schrödinger equation. When an electron
properties. It specifies the laws of motion that is in any energy state, the wave function

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 54 chemistry

corresponding to that energy state contains

all information about the electron. The wave 2. The existence of quantised electronic
energy levels is a direct result of the
function is a mathematical function whose
wave like properties of electrons and
value depends upon the coordinates of the are allowed solutions of Schrödinger
electron in the atom and does not carry any wave equation.
physical meaning. Such wave functions of 3. Both the exact position and exact
hydrogen or hydrogen like species with one velocity of an electron in an atom
electron are called atomic orbitals. Such cannot be determined simultaneously
wave functions pertaining to one-electron (Heisenberg uncertainty principle). The
species are called one-electron systems. The path of an electron in an atom therefore,
probability of finding an electron at a point can never be determined or known
within an atom is proportional to the |ψ|2 at accurately. That is why, as you shall see
later on, one talks of only probability of
that point. The quantum mechanical results
finding the electron at different points in
of the hydrogen atom successfully predict
an atom.
all aspects of the hydrogen atom spectrum 4. An atomic orbital is the wave
including some phenomena that could not be function ψ for an electron in an atom.
explained by the Bohr model. Whenever an electron is described
by a wave function, we say that the
Application of Schrödinger equation to
electron occupies that orbital. Since
multi-electron atoms presents a difficulty: the
many such wave functions are possible
Schrödinger equation cannot be solved exactly for an electron, there are many atomic
for a multi-electron atom. This difficulty can orbitals in an atom. These “one electron
be overcome by using approximate methods. orbital wave functions” or orbitals form
Such calculations with the aid of modern the basis of the electronic structure
computers show that orbitals in atoms other of atoms. In each orbital, the electron
than hydrogen do not differ in any radical has a definite energy. An orbital cannot
way from the hydrogen orbitals discussed contain more than two electrons. In a
above. The principal difference lies in the multi-electron atom, the electrons are
consequence of increased nuclear charge. filled in various orbitals in the order of
increasing energy. For each electron
Because of this all the orbitals are somewhat
of a multi-electron atom, there shall,
contracted. Further, as you shall see later (in therefore, be an orbital wave function
subsections 2.6.3 and 2.6.4), unlike orbitals characteristic of the orbital it occupies.
of hydrogen or hydrogen like species, whose All the information about the electron
energies depend only on the quantum number in an atom is stored in its orbital wave
n, the energies of the orbitals in multi-electron function ψ and quantum mechanics
atoms depend on quantum numbers n and l. makes it possible to extract this
information out of ψ.
Important Features of the Quantum 5. The probability of finding an electron at
Mechanical Model of Atom a point within an atom is proportional to
the square of the orbital wave function
Quantum mechanical model of atom is i.e., |ψ|2 at that point. |ψ|2 is known
the picture of the structure of the atom, as probability density and is always
which emerges from the application of positive. From the value of |ψ|2 at
the Schrödinger equation to atoms. The different points within an atom,
following are the important features of the it is possible to predict the region
quantum-mechanical model of atom: around the nucleus where electron
1. The energy of electrons in atoms is will most probably be found.
quantized (i.e., can only have certain
specific values), for example when 2.6.1 Orbitals and Quantum Numbers
electrons are bound to the nucleus in
atoms.
A large number of orbitals are possible in
an atom. Qualitatively these orbitals can

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be distinguished by their size, shape and sub-shells in a principal shell is equal to the
orientation. An orbital of smaller size means value of n. For example in the first shell (n = 1),
there is more chance of finding the electron there is only one sub-shell which corresponds
near the nucleus. Similarly shape and to l = 0. There are two sub-shells (l = 0, 1) in
orientation mean that there is more probability the second shell (n = 2), three (l = 0, 1, 2) in
of finding the electron along certain directions third shell (n = 3) and so on. Each sub-shell is
than along others. Atomic orbitals are precisely assigned an azimuthal quantum number (l).
distinguished by what are known as quantum Sub-shells corresponding to different values
numbers. Each orbital is designated by three of l are represented by the following symbols.
quantum numbers labelled as n, l and m l. Value for l : 0 1 2 3 4 5 ............
The principal quantum number ‘n’ is a notation for s p d f g h ............
positive integer with value of n = 1,2,3....... sub-shell
The principal quantum number determines Table 2.4 shows the permissible values of
the size and to large extent the energy of the ‘l ’ for a given principal quantum number and
orbital. For hydrogen atom and hydrogen like the corresponding sub-shell notation.
species (He+, Li2+, .... etc.) energy and size of
the orbital depends only on ‘n’. Table 2.4 Subshell Notations
The principal quantum number also n l Subshell notation
identifies the shell. With the increase in the
value of ‘n’, the number of allowed orbital 1 0 1s
increases and are given by ‘n 2’ All the
2 0 2s
orbitals of a given value of ‘n’ constitute
a single shell of atom and are represented 2 1 2p
by the following letters 3 0 3s
n = 1 2 3 4 ............
3 1 3p
Shell = K L M N ............
3 2 3d
Size of an orbital increases with increase of
principal quantum number ‘n’. In other words 4 0 4s
the electron will be located away from the
4 1 4p
nucleus. Since energy is required in shifting
away the negatively charged electron from the 4 2 4d
positively charged nucleus, the energy of the 4 3 4f
orbital will increase with increase of n.
Azimuthal quantum number. ‘l’ is also Magnetic orbital quantum number.
known as orbital angular momentum or ‘m l’ gives information about the spatial
subsidiary quantum number. It defines the orientation of the orbital with respect to
three-dimensional shape of the orbital. For a standard set of co-ordinate axis. For any
given value of n, l can have n values ranging sub-shell (defined by ‘l’ value) 2l+1 values of
from 0 to n – 1, that is, for a given value of n, ml are possible and these values are given by :
the possible value of l are : l = 0, 1, 2, .......... ml = – l, – (l –1), – (l– 2)... 0,1... (l – 2), (l–1), l
(n–1)
Thus for l = 0, the only permitted value
For example, when n = 1, value of l is only of ml = 0, [2(0)+1 = 1, one s orbital]. For l =
0. For n = 2, the possible value of l can be 0 1, ml can be –1, 0 and +1 [2(1)+1 = 3, three p
and 1. For n = 3, the possible l values are 0, orbitals]. For l = 2, ml = –2, –1, 0, +1 and +2,
1 and 2. [2(2)+1 = 5, five d orbitals]. It should be noted
Each shell consists of one or more that the values of ml are derived from l and
sub-shells or sub-levels. The number of that the value of l are derived from n.

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Each orbital in an atom, therefore, is angular momentum of the electron — a vector

defined by a set of values for n, l and ml. An quantity, can have two orientations relative to
orbital described by the quantum numbers the chosen axis. These two orientations are
n = 2, l = 1, ml = 0 is an orbital in the p sub- distinguished by the spin quantum numbers
shell of the second shell. The following chart ms which can take the values of +½ or –½.
gives the relation between the subshell and These are called the two spin states of the
the number of orbitals associated with it. electron and are normally represented by
Value of l 0 1 2 3 4 5 two arrows, ↑ (spin up) and ↓ (spin down). Two
Subshell notation s p d f g h electrons that have different ms values (one +½
and the other –½) are said to have opposite
number of orbitals 1 3 5 7 9 11 spins. An orbital cannot hold more than two
Electron spin ‘s’ : The three quantum electrons and these two electrons should have
numbers labelling an atomic orbital can be opposite spins.
used equally well to define its energy, shape To sum up, the four quantum numbers
and orientation. But all these quantum provide the following information :
numbers are not enough to explain the line i) n defines the shell, determines the size
spectra observed in the case of multi-electron of the orbital and also to a large extent
atoms, that is, some of the lines actually occur the energy of the orbital.
in doublets (two lines closely spaced), triplets
ii) There are n subshells in the nth shell. l
(three lines, closely spaced) etc. This suggests
identifies the subshell and determines
the presence of a few more energy levels than
the shape of the orbital (see section
predicted by the three quantum numbers.
2.6.2). There are (2l+1) orbitals of each
In 1925, George Uhlenbeck and Samuel type in a subshell, that is, one s orbital
Goudsmit proposed the presence of the fourth (l = 0), three p orbitals (l = 1) and five
quantum number known as the electron d orbitals (l = 2) per subshell. To some
spin quantum number (ms ). An electron extent l also determines the energy of
spins around its own axis, much in a similar the orbital in a multi-electron atom.
way as earth spins around its own axis while iii) ml designates the orientation of the
revolving around the sun. In other words, orbital. For a given value of l, ml has
an electron has, besides charge and mass, (2l+1) values, the same as the number
intrinsic spin angular quantum number. Spin of orbitals per subshell. It means that

Orbit, orbital and its importance

Orbit and orbital are not synonymous. An orbit, as proposed by Bohr, is a circular path around the
nucleus in which an electron moves. A precise description of this path of the electron is impossible
according to Heisenberg uncertainty principle. Bohr orbits, therefore, have no real meaning and
their existence can never be demonstrated experimentally. An atomic orbital, on the other hand,
is a quantum mechanical concept and refers to the one electron wave function ψ in an atom. It is
characterized by three quantum numbers (n, l and ml) and its value depends upon the coordinates
of the electron. ψ has, by itself, no physical meaning. It is the square of the wave function i.e., |ψ|2
which has a physical meaning. |ψ|2 at any point in an atom gives the value of probability density
at that point. Probability density (|ψ|2) is the probability per unit volume and the product of |ψ|2
and a small volume (called a volume element) yields the probability of finding the electron in that
volume (the reason for specifying a small volume element is that |ψ|2 varies from one region to
another in space but its value can be assumed to be constant within a small volume element).
The total probability of finding the electron in a given volume can then be calculated by the sum
of all the products of |ψ|2 and the corresponding volume elements. It is thus possible to get the
probable distribution of an electron in an orbital.

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the number of orbitals is equal to the

number of ways in which they are
oriented.
iv) ms refers to orientation of the spin of the
electron.

Problem 2.17
What is the total number of orbitals
associated with the principal quantum
number n = 3 ?
Solution
For n = 3, the possible values of l are
0, 1 and 2. Thus there is one 3s orbital
(n = 3, l = 0 and ml = 0); there are three
3p orbitals (n = 3, l = 1 and ml = –1, 0,
+1); there are five 3d orbitals (n = 3, l =
2 and ml = –2, –1, 0, +1+, +2). Fig. 2.12 The plots of (a) the orbital wave
Therefore, the total number of orbitals function ψ(r); (b) the variation of
is 1+3+5 = 9 probability density ψ2(r) as a function
of distance r of the electron from the
The same value can also be obtained by
nucleus for 1s and 2s orbitals.
using the relation; number of orbitals
= n2, i.e. 32 = 9.
According to the German physicist,
Problem 2.18 Max Born, the square of the wave function
(i.e.,ψ 2) at a point gives the probability density
Using s, p, d, f notations, describe the
of the electron at that point. The variation
orbital with the following quantum
numbers of ψ 2 as a function of r for 1s and 2s orbitals
is given in Fig. 2.12(b). Here again, you may
(a) n = 2, l = 1, (b) n = 4, l = 0, (c) n = 5,
note that the curves for 1s and 2s orbitals
l = 3, (d) n = 3, l = 2
are different.
Solution It may be noted that for 1s orbital the
n l orbital probability density is maximum at the
a) 2 1 2p nucleus and it decreases sharply as we move
away from it. On the other hand, for 2s
b) 4 0 4s
orbital the probability density first decreases
c) 5 3 5f sharply to zero and again starts increasing.
d) 3 2 3d After reaching a small maxima it decreases
again and approaches zero as the value of
r increases further. The region where this
2.6.2 Shapes of Atomic Orbitals probability density function reduces to zero
The orbital wave function or ψ for an electron is called nodal surfaces or simply nodes.
in an atom has no physical meaning. It In general, it has been found that ns-orbital
is simply a mathematical function of the has (n – 1) nodes, that is, number of nodes
coordinates of the electron. However, for increases with increase of principal quantum
different orbitals the plots of corresponding number n. In other words, number of nodes
wave functions as a function of r (the distance for 2s orbital is one, two for 3s and so on.
from the nucleus) are different. Fig. 2.12(a), These probability density variation can be
gives such plots for 1s (n = 1, l = 0) and 2s visualised in terms of charge cloud diagrams
(n = 2, l = 0) orbitals. [Fig. 2.13(a)]. In these diagrams, the density

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of the dots in a region represents electron

probability density in that region.
Boundary surface diagrams of constant
probability density for different orbitals give
a fairly good representation of the shapes
of the orbitals. In this representation, a
boundary surface or contour surface is
drawn in space for an orbital on which the
value of probability density |ψ|2 is constant.
In principle many such boundary surfaces
may be possible. However, for a given
orbital, only that boundary surface diagram
of constant probability density* is taken to
be good representation of the shape of the
orbital which encloses a region or volume in Fig. 2.13 (a) Probability density plots of 1s and
which the probability of finding the electron 2s atomic orbitals. The density of the
is very high, say, 90%. The boundary surface dots represents the probability density
diagram for 1s and 2s orbitals are given in of finding the electron in that region.
Fig. 2.13(b). One may ask a question : Why (b) Boundary surface diagram for 1s
do we not draw a boundary surface diagram, and 2s orbitals.
which bounds a region in which the probability
of finding the electron is, 100 %? The answer
to this question is that the probability density
| ψ | 2 has always some value, howsoever
small it may be, at any finite distance from
the nucleus. It is therefore, not possible to
draw a boundary surface diagram of a rigid
size in which the probability of finding the
electron is 100%. Boundary surface diagram
for a s orbital is actually a sphere centred on
the nucleus. In two dimensions, this sphere
looks like a circle. It encloses a region in
which probability of finding the electron is
about 90%.
Thus, we see that 1s and 2s orbitals are
spherical in shape. In reality all the s-orbitals
are spherically symmetric, that is, the
probability of finding the electron at a given Fig. 2.14 Boundary surface diagrams of the
distance is equal in all the directions. It is also three 2p orbitals.
observed that the size of the s orbital increases
with increase in n, that is, 4s > 3s > 2s > 1s these diagrams, the nucleus is at the origin.
and the electron is located further away from Here, unlike s-orbitals, the boundary surface
the nucleus as the principal quantum number diagrams are not spherical. Instead each
increases. p orbital consists of two sections called lobes
Boundary surface diagrams for three that are on either side of the plane that passes
2p orbitals (l = 1) are shown in Fig. 2.14. In through the nucleus. The probability density

* If probability density |ψ| is constant on a given surface, |ψ| is also constant over the surface. The boundary surface
2

for |ψ| and |ψ| are identical.

2

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 structure of atom 59

function is zero on the plane where the two it is sufficient to remember that, because
lobes touch each other. The size, shape and there are three possible values of m l, there
energy of the three orbitals are identical. are, therefore, three p orbitals whose axes
They differ however, in the way the lobes are are mutually perpendicular. Like s orbitals,
oriented. Since the lobes may be considered to p orbitals increase in size and energy with
lie along the x, y or z axis, they are given the increase in the principal quantum number
designations 2px, 2py, and 2pz. It should be and hence the order of the energy and size of
understood, however, that there is no simple various p orbitals is 4p > 3p > 2p. Further, like
relation between the values of ml (–1, 0 and +1) s orbitals, the probability density functions for
and the x, y and z directions. For our purpose, p-orbital also pass through value zero, besides
at zero and infinite distance, as the distance
from the nucleus increases. The number of
nodes are given by the n –2, that is number
of radial node is 1 for 3p orbital, two for 4p
orbital and so on.
For l = 2, the orbital is known as d-orbital
and the minimum value of principal quantum
number (n) has to be 3. as the value of l cannot
be greater than n–1. There are five ml values
(–2, –1, 0, +1 and +2) for l = 2 and thus there
are five d orbitals. The boundary surface
diagram of d orbitals are shown in Fig. 2.15.
The five d-orbitals are designated as dxy,
dyz, dxz, dx2–y2 and dz2. The shapes of the first
four d-orbitals are similar to each other, where
as that of the fifth one, dz2, is different from
others, but all five 3d orbitals are equivalent
in energy. The d orbitals for which n is greater
than 3 (4d, 5d...) also have shapes similar to
3d orbital, but differ in energy and size.
Besides the radial nodes (i.e., probability
density function is zero), the probability
density functions for the np and nd orbitals
are zero at the plane (s), passing through the
nucleus (origin). For example, in case of pz
orbital, xy-plane is a nodal plane, in case of
dxy orbital, there are two nodal planes passing
through the origin and bisecting the xy plane
containing z-axis. These are called angular
nodes and number of angular nodes are given
by ‘l’, i.e., one angular node for p orbitals, two
angular nodes for ‘d’ orbitals and so on. The
total number of nodes are given by (n–1),
i.e., sum of l angular nodes and (n – l – 1)
radial nodes.
2.6.3 Energies of Orbitals
Fig. 2.15 Boundary surface diagrams of the five The energy of an electron in a hydrogen atom
3d orbitals. is determined solely by the principal quantum

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 60 chemistry

number. Thus the energy of the orbitals in The energy of an electron in a multi-
hydrogen atom increases as follows : electron atom, unlike that of the hydrogen
1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d atom, depends not only on its principal
= 4f < (2 .23 ) quantum number (shell), but also on its
and is depicted in Fig. 2.16. Although the azimuthal quantum number (subshell). That
shapes of 2s and 2p orbitals are different, is, for a given principal quantum number, s,
an electron has the same energy when it is p, d, f ... all have different energies. Within
in the 2s orbital as when it is present in 2p a given principal quantum number, the
orbital. The orbitals having the same energy energy of orbitals increases in the order
are called degenerate. The 1s orbital in a s<p<d<f. For higher energy levels, these
differences are sufficiently pronounced and
hydrogen atom, as said earlier, corresponds
straggering of orbital energy may result,
to the most stable condition and is called the
e.g., 4s<3d and 6s<5d; 4f<6p. The main
ground state and an electron residing in this
reason for having different energies of the
orbital is most strongly held by the nucleus.
subshells is the mutual repulsion among the
An electron in the 2s, 2p or higher orbitals in
electrons in multi-electron atoms. The only
a hydrogen atom is in excited state.
electrical interaction present in hydrogen
atom is the attraction between the negatively
charged electron and the positively charged
nucleus. In multi-electron atoms, besides the
presence of attraction between the electron
and nucleus, there are repulsion terms
between every electron and other electrons
present in the atom. Thus the stability of an
electron in a multi-electron atom is because
total attractive interactions are more than
the repulsive interactions. In general, the
repulsive interaction of the electrons in the
outer shell with the electrons in the inner shell
are more important. On the other hand, the
attractive interactions of an electron increases
with increase of positive charge (Ze) on the
nucleus. Due to the presence of electrons in
the inner shells, the electron in the outer shell
will not experience the full positive charge of
the nucleus (Ze). The effect will be lowered
due to the partial screening of positive charge
on the nucleus by the inner shell electrons.
This is known as the shielding of the outer
Fig. 2.16 Energy level diagrams for the few shell electrons from the nucleus by the
electronic shells of (a) hydrogen atom inner shell electrons, and the net positive
and (b) multi-electronic atoms. Note that
charge experienced by the outer electrons is
orbitals for the same value of principal
quantum number, have the same known as effective nuclear charge (Zeff e).
energies even for different azimuthal Despite the shielding of the outer electrons
quantum number for hydrogen atom. from the nucleus by the inner shell electrons,
In case of multi-electron atoms, orbitals the attractive force experienced by the outer
with same principal quantum number shell electrons increases with increase of
possess different energies for different nuclear charge. In other words, the energy of
azimuthal quantum numbers.
interaction between, the nucleus and electron

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(that is orbital energy) decreases (that is Table 2.5 Arrangement of Orbitals with
more negative) with the increase of atomic Increasing Energy on the Basis
number (Z ). of (n+l ) Rule
Both the attractive and repulsive
interactions depend upon the shell and shape
of the orbital in which the electron is present.
For example electrons present in spherical
shaped, s orbital shields the outer electrons
from the nucleus more effectively as compared
to electrons present in p orbital. Similarly
electrons present in p orbitals shield the outer
electrons from the nucleus more than the
electrons present in d orbitals, even though all
these orbitals are present in the same shell.
Further within a shell, due to spherical shape
of s orbital, the s orbital electron spends more
time close to the nucleus in comparison to p
orbital electron which spends more time in
the vicinity of nucleus in comparison to d
orbital electron. In other words, for a given
shell (principal quantum number), the Zeff
experienced by the electron decreases with
increase of azimuthal quantum number (l),
that is, the s orbital electron will be more
tightly bound to the nucleus than p orbital
electron which in turn will be better tightly
bound than the d orbital electron. The energy
of electrons in s orbital will be lower (more
negative) than that of p orbital electron
which will have less energy than that of d
orbital electron and so on. Since the extent same energy. Lastly it may be mentioned here
of shielding from the nucleus is different for that energies of the orbitals in the same
electrons in different orbitals, it leads to the subshell decrease with increase in the
splitting of energy levels within the same atomic number (Zeff). For example, energy of
shell (or same principal quantum number), 2s orbital of hydrogen atom is greater than
that is, energy of electron in an orbital, as that of 2s orbital of lithium and that of lithium
mentioned earlier, depends upon the values is greater than that of sodium and so on, that
of n and l. Mathematically, the dependence is, E2s(H) > E2s(Li) > E2s(Na) > E2s(K).
of energies of the orbitals on n and l are quite
complicated but one simple rule is that, the 2.6.4 Filling of Orbitals in Atom
lower the value of (n + l) for an orbital, the The filling of electrons into the orbitals of
lower is its energy. If two orbitals have different atoms takes place according to
the same value of (n + l), the orbital with the aufbau principle which is based on the
lower value of n will have the lower energy. Pauli’s exclusion principle, the Hund’s rule
The Table 2.5 illustrates the (n + l ) rule and of maximum multiplicity and the relative
Fig. 2.16 depicts the energy levels of multi- energies of the orbitals.
electrons atoms. It may be noted that different
subshells of a particular shell have different Aufbau Principle
energies in case of multi-electrons atoms. The word ‘aufbau’ in German means ‘building
However, in hydrogen atom, these have the up’. The building up of orbitals means the

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filling up of orbitals with electrons. The the top, the direction of the arrows gives the
principle states : In the ground state of the order of filling of orbitals, that is starting
atoms, the orbitals are filled in order of from right top to bottom left. With respect to
their increasing energies. In other words, placement of outermost valence electrons,
electrons first occupy the lowest energy orbital it is remarkably accurate for all atoms. for
available to them and enter into higher energy example, valence electron in potassium
orbitals only after the lower energy orbitals must choose between 3d and 4s orbitals and
are filled. As you have learnt above, energy as predicted by this sequence, it is found
of a given orbital depends upon effective in 4s orbital. The above order should be
nuclear charge and different type of orbitals assumed to be a rough guide to the filling
are affected to different extent. Thus, there of energy levels. In many cases, the orbitals
is no single ordering of energies of orbitals are similar in energy and small changes in
which will be universally correct for all atoms. atomic structure may bring about a change
in the order of filling. Even then, the above
However, following order of energies of
series is a useful guide to the building of the
the orbitals is extremely useful:
electronic structure of an atom provided that
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f,
it is remembered that exceptions may occur.
5d, 6p, 7s...
Pauli Exclusion Principle
The order may be remembered by using
the method given in Fig. 2.17. Starting from The number of electrons to be filled in various
orbitals is restricted by the exclusion principle,
given by the Austrian scientist Wolfgang Pauli
(1926). According to this principle : No two
electrons in an atom can have the same set
of four quantum numbers. Pauli exclusion
principle can also be stated as : “Only two
electrons may exist in the same orbital and
these electrons must have opposite spin.”
This means that the two electrons can have
the same value of three quantum numbers
n, l and ml, but must have the opposite spin
quantum number. The restriction imposed
by Pauli’s exclusion principle on the number
of electrons in an orbital helps in calculating
the capacity of electrons to be present in any
subshell. For example, subshell 1s comprises
one orbital and thus the maximum number of
electrons present in 1s subshell can be two, in
p and d subshells, the maximum number of
electrons can be 6 and 10 and so on. This can
be summed up as : the maximum number
of electrons in the shell with principal
quantum number n is equal to 2n2.
Hund’s Rule of Maximum Multiplicity
This rule deals with the filling of electrons into
the orbitals belonging to the same subshell
(that is, orbitals of equal energy, called
Fig.2.17 Order of filling of orbitals degenerate orbitals). It states : pairing of

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electrons in the orbitals belonging to the 1s orbital. Its configuration is, therefore, 1s2.
same subshell (p, d or f) does not take As mentioned above, the two electrons differ
place until each orbital belonging to that from each other with opposite spin, as can be
subshell has got one electron each i.e., it seen from the orbital diagram.
is singly occupied.
Since there are three p, five d and seven f
orbitals, therefore, the pairing of electrons will The third electron of lithium (Li) is not
start in the p, d and f orbitals with the entry allowed in the 1s orbital because of Pauli
of 4th, 6th and 8th electron, respectively. It exclusion principle. It, therefore, takes the
has been observed that half filled and fully next available choice, namely the 2s orbital.
filled degenerate set of orbitals acquire extra The electronic configuration of Li is 1s22s1.
stability due to their symmetry (see Section, The 2s orbital can accommodate one more
2.6.7). electron. The configuration of beryllium (Be)
2.6.5 Electronic Configuration of Atoms atom is, therefore, 1s2 2s2 (see Table 2.6,
page 66 for the electronic configurations of
The distribution of electrons into orbitals of an
elements).
atom is called its electronic configuration.
If one keeps in mind the basic rules which In the next six elements—boron
govern the filling of different atomic orbitals, (B, 1s22s22p1), carbon (C, 1s22s22p2), nitrogen
the electronic configurations of different (N, 1s22s22p3), oxygen (O, 1s22s22p4), fluorine
atoms can be written very easily. (F, 1s22s22p5) and neon (Ne, 1s22s22p6), the 2p
orbitals get progressively filled. This process
The electronic configuration of different is completed with the neon atom. The orbital
atoms can be represented in two ways. For picture of these elements can be represented
example : as follows :
(i) sa pbdc ...... notation
(ii) Orbital diagram

s p d
In the first notation, the subshell is
represented by the respective letter symbol
and the number of electrons present in the
subshell is depicted, as the super script, like
a, b, c, ... etc. The similar subshell represented
for different shells is differentiated by writing
the principal quantum number before the
respective subshell. In the second notation
each orbital of the subshell is represented
by a box and the electron is represented by
an arrow (↑) a positive spin or an arrow (↓) The electronic configuration of the
a negative spin. The advantage of second elements sodium (Na, 1s22s22p63s1) to argon
notation over the first is that it represents all (Ar,1s22s22p63s23p6), follow exactly the same
the four quantum numbers. pattern as the elements from lithium to neon
The hydrogen atom has only one electron with the difference that the 3s and 3p orbitals
which goes in the orbital with the lowest energy, are getting filled now. This process can be
namely 1s. The electronic configuration of the simplified if we represent the total number
hydrogen atom is 1s1 meaning that it has of electrons in the first two shells by the
one electron in the 1s orbital. The second name of element neon (Ne). The electronic
electron in helium (He) can also occupy the configuration of the elements from sodium to

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argon can be written as (Na, [Ne]3s1) to (Ar, After this, filling of 6p, then 7s and finally 5f
[Ne] 3s23p6). The electrons in the completely and 6d orbitals takes place. The elements
filled shells are known as core electrons and after uranium (U) are all short-lived and all of
the electrons that are added to the electronic them are produced artificially. The electronic
shell with the highest principal quantum configurations of the known elements (as
number are called valence electrons. For determined by spectroscopic methods) are
example, the electrons in Ne are the core tabulated in Table 2.6 (page 66).
electrons and the electrons from Na to Ar are One may ask what is the utility of knowing
the valence electrons. In potassium (K) and the electron configuration? The modern
calcium (Ca), the 4s orbital, being lower in approach to the chemistry, infact, depends
energy than the 3d orbitals, is occupied by almost entirely on electronic distribution to
one and two electrons respectively.
understand and explain chemical behaviour.
A new pattern is followed beginning with For example, questions like why two or more
scandium (Sc). The 3d orbital, being lower atoms combine to form molecules, why some
in energy than the 4p orbital, is filled first. elements are metals while others are non-
Consequently, in the next ten elements, metals, why elements like helium and argon
scandium (Sc), titanium (Ti), vanadium (V), are not reactive but elements like the halogens
chromium (Cr), manganese (Mn), iron (Fe), are reactive, find simple explanation from the
cobalt (Co), nickel (Ni), copper (Cu) and zinc electronic configuration. These questions have
(Zn), the five 3d orbitals are progressively no answer in the Daltonian model of atom.
occupied. We may be puzzled by the fact A detailed understanding of the electronic
that chromium and copper have five and ten
structure of atom is, therefore, very essential
electrons in 3d orbitals rather than four and
for getting an insight into the various aspects
nine as their position would have indicated
of modern chemical knowledge.
with two-electrons in the 4s orbital. The
reason is that fully filled orbitals and half- 2.6.6 Stability of Completely Filled and
filled orbitals have extra stability (that is, Half Filled Subshells
lower energy). Thus p3, p6, d5, d10,f 7, f14 etc. The ground state electronic configuration of
configurations, which are either half-filled the atom of an element always corresponds to
or fully filled, are more stable. Chromium the state of the lowest total electronic energy.
and copper therefore adopt the d 5 and The electronic configurations of most of the
d 10 configuration (Section 2.6.7)[caution: atoms follow the basic rules given in Section
exceptions do exist] 2.6.5. However, in certain elements such as
With the saturation of the 3d orbitals, Cu, or Cr, where the two subshells (4s and
the filling of the 4p orbital starts at gallium 3d) differ slightly in their energies, an electron
(Ga) and is complete at krypton (Kr). In the shifts from a subshell of lower energy (4s) to a
next eighteen elements from rubidium (Rb) subshell of higher energy (3d), provided such
to xenon (Xe), the pattern of filling the 5s, a shift results in all orbitals of the subshell
4d and 5p orbitals are similar to that of 4s, of higher energy getting either completely
3d and 4p orbitals as discussed above. Then filled or half filled. The valence electronic
comes the turn of the 6s orbital. In caesium configurations of Cr and Cu, therefore, are
(Cs) and the barium (Ba), this orbital contains 3d5 4s1 and 3d10 4s1 respectively and not 3d4
one and two electrons, respectively. Then from 4s2 and 3d9 4s2. It has been found that there is
lanthanum (La) to mercury (Hg), the filling up extra stability associated with these electronic
of electrons takes place in 4f and 5d orbitals. configurations.

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Causes of Stability of Completely Filled and Half-filled Subshells

The completely filled and completely

half-filled subshells are stable due to the
following reasons:
1. Symmetrical distribution of
electrons: It is well known that symmetry
leads to stability. The completely filled
or half filled subshells have symmetrical
distribution of electrons in them and
are therefore more stable. Electrons in
the same subshell (here 3d) have equal
energy but different spatial distribution.
Consequently, their shielding of one-
another is relatively small and the
electrons are more strongly attracted by
the nucleus.
2. Exchange Energy : The stabilizing
effect arises whenever two or more
electrons with the same spin are present
in the degenerate orbitals of a subshell.
These electrons tend to exchange their
positions and the energy released due to
this exchange is called exchange energy.
The number of exchanges that can take
place is maximum when the subshell
is either half filled or completely filled
(Fig. 2.18). As a result the exchange
energy is maximum and so is the stability.
You may note that the exchange
energy is at the basis of Hund’s rule
that electrons which enter orbitals of
equal energy have parallel spins as far
as possible. In other words, the extra
stability of half-filled and completely filled
subshell is due to: (i) relatively small
shielding, (ii) smaller coulombic repulsion
energy, and (iii) larger exchange energy.
Details about the exchange energy will be Fig. 2.18 Possible exchange for a d5
dealt with in higher classes. configuration

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Table 2.6 Electronic Configurations of the Elements

* Elements with exceptional electronic configurations

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** Elements with atomic number 112 and above have been reported but not yet fully authenticated and named.

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Summary

Atoms are the building blocks of elements. They are the smallest parts of an element that
chemically react. The first atomic theory, proposed by John Dalton in 1808, regarded atom as
the ultimate indivisible particle of matter. Towards the end of the nineteenth century, it was
proved experimentally that atoms are divisible and consist of three fundamental particles:
electrons, protons and neutrons. The discovery of sub-atomic particles led to the proposal
of various atomic models to explain the structure of atom.
Thomson in 1898 proposed that an atom consists of uniform sphere of positive electricity
with electrons embedded into it. This model in which mass of the atom is considered to
be evenly spread over the atom was proved wrong by Rutherford’s famous alpha-particle
scattering experiment in 1909. Rutherford concluded that atom is made of a tiny positively
charged nucleus, at its centre with electrons revolving around it in circular orbits.
Rutherford model, which resembles the solar system, was no doubt an improvement over
Thomson model but it could not account for the stability of the atom i.e., why the electron
does not fall into the nucleus. Further, it was also silent about the electronic structure of
atoms i.e., about the distribution and relative energies of electrons around the nucleus. The
difficulties of the Rutherford model were overcome by Niels Bohr in 1913 in his model of the
hydrogen atom. Bohr postulated that electron moves around the nucleus in circular orbits.
Only certain orbits can exist and each orbit corresponds to a specific energy. Bohr calculated
the energy of electron in various orbits and for each orbit predicted the distance between the
electron and nucleus. Bohr model, though offering a satisfactory model for explaining the
spectra of the hydrogen atom, could not explain the spectra of multi-electron atoms. The
reason for this was soon discovered. In Bohr model, an electron is regarded as a charged
particle moving in a well defined circular orbit about the nucleus. The wave character of
the electron is ignored in Bohr’s theory. An orbit is a clearly defined path and this path can
completely be defined only if both the exact position and the exact velocity of the electron
at the same time are known. This is not possible according to the Heisenberg uncertainty
principle. Bohr model of the hydrogen atom, therefore, not only ignores the dual behaviour
of electron but also contradicts Heisenberg uncertainty principle.
Erwin Schrödinger, in 1926, proposed an equation called Schrödinger equation to
describe the electron distributions in space and the allowed energy levels in atoms. This
equation incorporates de Broglie’s concept of wave-particle duality and is consistent with
Heisenberg uncertainty principle. When Schrödinger equation is solved for the electron in a
hydrogen atom, the solution gives the possible energy states the electron can occupy [and
the corresponding wave function(s) (ψ) (which in fact are the mathematical functions) of the
electron associated with each energy state]. These quantized energy states and corresponding
wave functions which are characterized by a set of three quantum numbers (principal
quantum number n, azimuthal quantum number l and magnetic quantum number ml)
arise as a natural consequence in the solution of the Schrödinger equation. The restrictions
on the values of these three quantum numbers also come naturally from this solution. The
quantum mechanical model of the hydrogen atom successfully predicts all aspects of the
hydrogen atom spectrum including some phenomena that could not be explained by the
Bohr model.
According to the quantum mechanical model of the atom, the electron distribution of an
atom containing a number of electrons is divided into shells. The shells, in turn, are thought
to consist of one or more subshells and subshells are assumed to be composed of one or
more orbitals, which the electrons occupy. While for hydrogen and hydrogen like systems
(such as He+, Li2+ etc.) all the orbitals within a given shell have same energy, the energy of
the orbitals in a multi-electron atom depends upon the values of n and l: The lower the value
of (n + l ) for an orbital, the lower is its energy. If two orbitals have the same (n + l ) value,
the orbital with lower value of n has the lower energy. In an atom many such orbitals are

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possible and electrons are filled in those orbitals in order of increasing energy in accordance
with Pauli exclusion principle (no two electrons in an atom can have the same set of four
quantum numbers) and Hund’s rule of maximum multiplicity (pairing of electrons in the
orbitals belonging to the same subshell does not take place until each orbital belonging to
that subshell has got one electron each, i.e., is singly occupied). This forms the basis of the
electronic structure of atoms.

EXERCISES

2.1 (i) Calculate the number of electrons which will together weigh one gram.
(ii) Calculate the mass and charge of one mole of electrons.
2.2 (i) Calculate the total number of electrons present in one mole of methane.
(ii) Find (a) the total number and (b) the total mass of neutrons in 7 mg of 14C.
(Assume that mass of a neutron = 1.675 × 10–27 kg).
(iii) Find (a) the total number and (b) the total mass of protons in 34 mg of NH3
at STP.
Will the answer change if the temperature and pressure are changed ?
2.3 How many neutrons and protons are there in the following nuclei ?
13 16 24 56 88
6 C, 8 O, 12 Mg, 26 Fe, 38 Sr

2.4 Write the complete symbol for the atom with the given atomic number (Z) and atomic
mass (A)
(i) Z = 17, A = 35.
(ii) Z = 92, A = 233.
(iii) Z = 4, A = 9.
2.5 Yellow light emitted from a sodium lamp has a wavelength (λ) of 580 nm. Calculate
the frequency (ν) and wavenumber ( ) of the yellow light.
2.6 Find energy of each of the photons which
(i) correspond to light of frequency 3×1015 Hz.
(ii) have wavelength of 0.50 Å.
2.7 Calculate the wavelength, frequency and wavenumber of a light wave whose period
is 2.0 × 10–10 s.
2.8 What is the number of photons of light with a wavelength of 4000 pm that provide
1J of energy?
2.9 A photon of wavelength 4 × 10–7 m strikes on metal surface, the work function
of the metal being 2.13 eV. Calculate (i) the energy of the photon (eV),
(ii) the kinetic energy of the emission, and (iii) the velocity of the photoelectron
(1 eV= 1.6020 × 10–19 J).
2.10 Electromagnetic radiation of wavelength 242 nm is just sufficient to ionise the
sodium atom. Calculate the ionisation energy of sodium in kJ mol–1.
2.11 A 25 watt bulb emits monochromatic yellow light of wavelength of 0.57µm.
Calculate the rate of emission of quanta per second.
2.12 Electrons are emitted with zero velocity from a metal surface when it is exposed to
radiation of wavelength 6800 Å. Calculate threshold frequency (ν0 ) and work function
(W0 ) of the metal.
2.13 What is the wavelength of light emitted when the electron in a hydrogen atom undergoes
transition from an energy level with n = 4 to an energy level with n = 2?

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2.14 How much energy is required to ionise a H atom if the electron occupies n = 5 orbit?
Compare your answer with the ionization enthalpy of H atom (energy required to
remove the electron from n =1 orbit).
2.15 What is the maximum number of emission lines when the excited electron of a H
atom in n = 6 drops to the ground state?
2.16 (i) The energy associated with the first orbit in the hydrogen atom is
–2.18 × 10–18 J atom–1. What is the energy associated with the fifth orbit?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.
2.17 Calculate the wavenumber for the longest wavelength transition in the Balmer series
of atomic hydrogen.
2.18 What is the energy in joules, required to shift the electron of the hydrogen atom from
the first Bohr orbit to the fifth Bohr orbit and what is the wavelength of the light
emitted when the electron returns to the ground state? The ground state electron
energy is –2.18 × 10–11 ergs.
2.19 The electron energy in hydrogen atom is given by En = (–2.18 × 10–18 )/n2 J. Calculate
the energy required to remove an electron completely from the n = 2 orbit. What is
the longest wavelength of light in cm that can be used to cause this transition?
2.20 Calculate the wavelength of an electron moving with a velocity of 2.05 × 107 m s–1.
2.21 The mass of an electron is 9.1 × 10–31 kg. If its K.E. is 3.0 × 10–25 J, calculate its
wavelength.
2.22 Which of the following are isoelectronic species i.e., those having the same number
of electrons?
Na+, K+, Mg2+, Ca2+, S2–, Ar.
2.23 (i) Write the electronic configurations of the following ions: (a) H– (b) Na+ (c) O2–
(d) F–
(ii) What are the atomic numbers of elements whose outermost electrons are
represented by (a) 3s1 (b) 2p3 and (c) 3p5 ?
(iii) Which atoms are indicated by the following configurations ?
(a) [He] 2s1 (b) [Ne] 3s2 3p3 (c) [Ar] 4s2 3d1.
2.24 What is the lowest value of n that allows g orbitals to exist?
2.25 An electron is in one of the 3d orbitals. Give the possible values of n, l and ml for
this electron.
2.26 An atom of an element contains 29 electrons and 35 neutrons. Deduce (i) the number
of protons and (ii) the electronic configuration of the element.
2.27 Give the number of electrons in the species
2.28 (i) An atomic orbital has n = 3. What are the possible values of l and ml ?
(ii) List the quantum numbers (ml and l) of electrons for 3d orbital.
(iii) Which of the following orbitals are possible?
1p, 2s, 2p and 3f
2.29 Using s, p, d notations, describe the orbital with the following quantum numbers.
(a) n=1, l=0; (b) n = 3; l=1 (c) n = 4; l =2; (d) n=4; l=3.
2.30 Explain, giving reasons, which of the following sets of quantum numbers are not
possible.
(a) n = 0, l = 0, ml = 0, ms = + ½
(b) n = 1, l = 0, ml = 0, ms = – ½
(c) n = 1, l = 1, ml = 0, ms = + ½
(d) n = 2, l = 1, ml = 0, ms = – ½

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 structure of atom 71

(e) n = 3, l = 3, ml = –3, ms = + ½
(f) n = 3, l = 1, ml = 0, ms = + ½
2.31 How many electrons in an atom may have the following quantum numbers?
(a) n = 4, ms = – ½ (b) n = 3, l = 0
2.32 Show that the circumference of the Bohr orbit for the hydrogen atom is an integral
multiple of the de Broglie wavelength associated with the electron revolving around
the orbit.
2.33 What transition in the hydrogen spectrum would have the same wavelength as the
Balmer transition n = 4 to n = 2 of He+ spectrum ?
2.34 Calculate the energy required for the process
He+ (g)  He2+ (g) + e–
The ionization energy for the H atom in the ground state is 2.18 × 10–18 J atom–1
2.35 If the diameter of a carbon atom is 0.15 nm, calculate the number of carbon atoms
which can be placed side by side in a straight line across length of scale of length
20 cm long.
2.36 2 ×108 atoms of carbon are arranged side by side. Calculate the radius of carbon
atom if the length of this arrangement is 2.4 cm.
2.37 The diameter of zinc atom is 2.6 Å. Calculate (a) radius of zinc atom in pm and
(b) number of atoms present in a length of 1.6 cm if the zinc atoms are arranged
side by side lengthwise.
2.38 A certain particle carries 2.5 × 10–16C of static electric charge. Calculate the number
of electrons present in it.
2.39 In Milikan’s experiment, static electric charge on the oil drops has been obtained
by shining X-rays. If the static electric charge on the oil drop is –1.282 × 10–18C,
calculate the number of electrons present on it.
2.40 In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold, platinum
etc. have been used to be bombarded by the α-particles. If the thin foil of light atoms
like aluminium etc. is used, what difference would be observed from the above
results ?
79 35
2.41 Symbols 35 Br
and 79
Br can be written, whereas symbols 79 Br
and 35
Br are not
acceptable. Answer briefly.
2.42 An element with mass number 81 contains 31.7% more neutrons as compared to
protons. Assign the atomic symbol.
2.43 An ion with mass number 37 possesses one unit of negative charge. If the ion
conatins 11.1% more neutrons than the electrons, find the symbol of the ion.
2.44 An ion with mass number 56 contains 3 units of positive charge and 30.4% more
neutrons than electrons. Assign the symbol to this ion.
2.45 Arrange the following type of radiations in increasing order of frequency: (a) radiation
from microwave oven (b) amber light from traffic signal (c) radiation from FM radio
(d) cosmic rays from outer space and (e) X-rays.
2.46 Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of
photons emitted is 5.6 × 1024, calculate the power of this laser.
2.47 Neon gas is generally used in the sign boards. If it emits strongly at 616 nm,
calculate (a) the frequency of emission, (b) distance traveled by this radiation in
30 s (c) energy of quantum and (d) number of quanta present if it produces 2 J of
energy.

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2.48 In astronomical observations, signals observed from the distant stars are generally
weak. If the photon detector receives a total of 3.15 × 10–18 J from the radiations of
600 nm, calculate the number of photons received by the detector.
2.49 Lifetimes of the molecules in the excited states are often measured by using pulsed
radiation source of duration nearly in the nano second range. If the radiation source
has the duration of 2 ns and the number of photons emitted during the pulse source
is 2.5 × 1015, calculate the energy of the source.
2.50 The longest wavelength doublet absorption transition is observed at 589 and 589.6
nm. Calcualte the frequency of each transition and energy difference between two
excited states.
2.51 The work function for caesium atom is 1.9 eV. Calculate (a) the threshold wavelength
and (b) the threshold frequency of the radiation. If the caesium element is irradiated
with a wavelength 500 nm, calculate the kinetic energy and the velocity of the ejected
photoelectron.
2.52 Following results are observed when sodium metal is irradiated with different
wavelengths. Calculate (a) threshold wavelength and, (b) Planck’s constant.
λ (nm) 500 450 400
v × 10–5 (cm s–1) 2.55 4.35 5.35
2.53 The ejection of the photoelectron from the silver metal in the photoelectric effect
experiment can be stopped by applying the voltage of 0.35 V when the radiation
256.7 nm is used. Calculate the work function for silver metal.
2.54 If the photon of the wavelength 150 pm strikes an atom and one of tis inner bound
electrons is ejected out with a velocity of 1.5 × 107 m s–1, calculate the energy with
which it is bound to the nucleus.
2.55 Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n
and can be represeted as v = 3.29 × 1015 (Hz) [1/32 – 1/n2]
Calculate the value of n if the transition is observed at 1285 nm. Find the region of
the spectrum.
2.56 Calculate the wavelength for the emission transition if it starts from the orbit having
radius 1.3225 nm and ends at 211.6 pm. Name the series to which this transition
belongs and the region of the spectrum.
2.57 Dual behaviour of matter proposed by de Broglie led to the discovery of electron
microscope often used for the highly magnified images of biological molecules and
other type of material. If the velocity of the electron in this microscope is 1.6 × 106
ms–1, calculate de Broglie wavelength associated with this electron.
2.58 Similar to electron diffraction, neutron diffraction microscope is also used for the
determination of the structure of molecules. If the wavelength used here is 800 pm,
calculate the characteristic velocity associated with the neutron.
2.59 If the velocity of the electron in Bohr’s first orbit is 2.19 × 106 ms–1, calculate the
de Broglie wavelength associated with it.
2.60 The velocity associated with a proton moving in a potential difference of 1000 V
is 4.37 × 105 ms–1. If the hockey ball of mass 0.1 kg is moving with this velocity,
calcualte the wavelength associated with this velocity.
2.61 If the position of the electron is measured within an accuracy of + 0.002 nm, calculate
the uncertainty in the momentum of the electron. Suppose the momentum of the
electron is h/4πm × 0.05 nm, is there any problem in defining this value.
2.62 The quantum numbers of six electrons are given below. Arrange them in order of
increasing energies. If any of these combination(s) has/have the same energy lists:
1. n = 4, l = 2, ml = –2 , ms = –1/2
2. n = 3, l = 2, ml = 1 , ms = +1/2

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 structure of atom 73

3. n = 4, l = 1, ml = 0 , ms = +1/2
4. n = 3, l = 2, ml = –2 , ms = –1/2
5. n = 3, l = 1, ml = –1 , ms = +1/2
6. n = 4, l = 1, ml = 0 , ms = +1/2
2.63 The bromine atom possesses 35 electrons. It contains 6 electrons in 2p orbital,
6 electrons in 3p orbital and 5 electron in 4p orbital. Which of these electron
experiences the lowest effective nuclear charge ?
2.64 Among the following pairs of orbitals which orbital will experience the larger effective
nuclear charge? (i) 2s and 3s, (ii) 4d and 4f, (iii) 3d and 3p.
2.65 The unpaired electrons in Al and Si are present in 3p orbital. Which electrons will
experience more effective nuclear charge from the nucleus ?
2.66 Indicate the number of unpaired electrons in : (a) P, (b) Si, (c) Cr, (d) Fe and (e) Kr.
2.67 (a) How many subshells are associated with n = 4 ? (b) How many electrons will be
present in the subshells having ms value of –1/2 for n = 4 ?

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 Unit 3

Classification of Elements and

Periodicity in Properties

The Periodic Table is arguably the most important concept

in chemistry, both in principle and in practice. It is the
everyday support for students, it suggests new avenues
of research to professionals, and it provides a succinct
After studying this Unit, you will be organization of the whole of chemistry. It is a remarkable
able to demonstration of the fact that the chemical elements are
not a random cluster of entities but instead display trends
• appreciate how the concept of
and lie together in families. An awareness of the Periodic
grouping elements in accordance
Table is essential to anyone who wishes to disentangle
to their properties led to the
the world and see how it is built up from the fundamental
development of Periodic Table.
building blocks of the chemistry, the chemical elements.
• understand the Periodic Law;
• understand the significance of Glenn T. Seaborg
atomic number and electronic
configuration as the basis for
periodic classification;
In this Unit, we will study the historical development of the
• name the elements with
Z >100 according to IUPAC
Periodic Table as it stands today and the Modern Periodic
nomenclature; Law. We will also learn how the periodic classification
follows as a logical consequence of the electronic
• classify elements into s, p, d,
f blocks and learn their main configuration of atoms. Finally, we shall examine some of
characteristics; the periodic trends in the physical and chemical properties
• recognise the periodic trends in of the elements.
physical and chemical properties
of elements;
3.1 WHY DO WE NEED TO CLASSIFY ELEMENTS ?
• compare the reactivity of elements We know by now that the elements are the basic units of
and correlate it with their all types of matter. In 1800, only 31 elements were known.
occurrence in nature; By  1865, the number of identified elements had more than
• explain the relationship between doubled to 63. At present 114 elements are known. Of
ionization enthalpy and metallic them, the recently discovered elements are man-made.
character; Efforts to synthesise new elements are continuing. With
• use scientific vocabulary such a large number of elements it is very difficult to
appropriately to communicate study individually the chemistry of all these elements and
ideas related to certain important their innumerable compounds individually. To ease out
properties of atoms e.g., this problem, scientists searched for a systematic way to
atomic/ionic radii, ionization
organise their knowledge by classifying the elements. Not
enthalpy, electron gain enthalpy,
electronegativity, valence of only that it would rationalize known chemical facts about
elements. elements, but even predict new ones for undertaking
further study.

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 Classification of Elements and Periodicity in Properties 75

3.2 GENESIS OF PERIODIC the periodic recurrence of properties. This

CLASSIFICATION also did not attract much attention. The
Classification of elements into groups and English chemist, John Alexander Newlands
development of Periodic Law and Periodic in 1865 profounded the Law of Octaves. He
Table are the consequences of systematising arranged the elements in increasing order
the knowledge gained by a number of of their atomic weights and noted that every
scientists through their observations and eighth element had properties similar to the
experiments. The German chemist, Johann first element (Table 3.2). The relationship was
Dobereiner in early 1800’s was the first to just like every eighth note that resembles the
consider the idea of trends among properties first in octaves of music. Newlands’s Law of
of elements. By 1829 he noted a similarity Octaves seemed to be true only for elements
among the physical and chemical properties up to calcium. Although his idea was not
of several groups of three elements (Triads). In widely accepted at that time, he, for his work,
each case, he noticed that the middle element was later awarded Davy Medal in 1887 by the
of each of the Triads had an atomic weight Royal Society, London.
about half way between the atomic weights of The Periodic Law, as we know it today
the other two (Table 3.1). Also the properties owes its development to the Russian chemist,
of the middle element were in between those Dmitri Mendeleev (1834-1907) and the
of the other two members. Since Dobereiner’s German chemist, Lothar Meyer (1830-1895).

Table 3.1 Dobereiner’s Triads

Atomic Atomic Atomic

Element Element Element
weight weight weight

Li 7 Ca 40 Cl 35.5
Na 23 Sr 88 Br 80
K 39 Ba 137 I 127

relationship, referred to as the Law of Triads, Working independently, both the chemists in
seemed to work only for a few elements, it was 1869 proposed that on arranging elements in
dismissed as coincidence. The next reported the increasing order of their atomic weights,
attempt to classify elements was made by a similarities appear in physical and chemical
French geologist, A.E.B. de Chancourtois in properties at regular intervals. Lothar Meyer
1862. He arranged the then known elements plotted the physical properties such as
in order of increasing atomic weights and atomic volume, melting point and boiling
made a cylindrical table of elements to display point against atomic weight and obtained

Table 3.2 Newlands’ Octaves

Element Li Be B C N O F
At. wt. 7 9 11 12 14 16 19
Element Na Mg Al Si P S Cl
At. wt. 23 24 27 29 31 32 35.5
Element K Ca
At. wt. 39 40

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 76 chemistry

a periodically repeated pattern. Unlike classification if the order of atomic weight

Newlands, Lothar Meyer observed a change was strictly followed. He ignored the order
in length of that repeating pattern. By 1868, of atomic weights, thinking that the atomic
Lothar Meyer had developed a table of the measurements might be incorrect, and placed
elements that closely resembles the Modern the elements with similar properties together.
Periodic Table. However, his work was not For example, iodine with lower atomic weight
published until after the work of Dmitri than that of tellurium (Group VI) was placed
Mendeleev, the scientist who is generally in Group VII along with fluorine, chlorine,
credited with the development of the Modern bromine because of similarities in properties
Periodic Table. (Fig. 3.1). At the same time, keeping his
While Dobereiner initiated the study of primary aim of arranging the elements of
periodic relationship, it was Mendeleev who similar properties in the same group, he
was responsible for publishing the Periodic proposed that some of the elements were
Law for the first time. It states as follows : still undiscovered and, therefore, left several
gaps in the table. For example, both gallium
The properties of the elements are and germanium were unknown at the time
a periodic function of their atomic
Mendeleev published his Periodic Table.
weights.
He left the gap under aluminium and a gap
Mendeleev arranged elements in horizontal under silicon, and called these elements
rows and vertical columns of a table in order Eka-Aluminium and Eka-Silicon. Mendeleev
of their increasing atomic weights in such a predicted not only the existence of gallium and
way that the elements with similar properties germanium, but also described some of their
occupied the same vertical column or group. general physical properties. These elements
Mendeleev’s system of classifying elements were discovered later. Some of the properties
was more elaborate than that of Lothar predicted by Mendeleev for these elements
Meyer’s. He fully recognized the significance and those found experimentally are listed in
of periodicity and used broader range of Table 3.3.
physical and chemical properties to classify
the elements. In particular, Mendeleev relied The boldness of Mendeleev’s quantitative
on the similarities in the empirical formulas predictions and their eventual success
and properties of the compounds formed by made him and his Periodic Table famous.
the elements. He realized that some of the Mendeleev’s Periodic Table published in 1905
elements did not fit in with his scheme of is shown in Fig. 3.1.

Table 3.3 Mendeleev’s Predictions for the Elements Eka-aluminium (Gallium) and
Eka-silicon (Germanium)

Eka-aluminium Gallium Eka-silicon Germanium

Property
(predicted) (found) (predicted) (found)

Atomic weight 68 70 72 72.6

Density/(g/cm3) 5.9 5.94 5.5 5.36

Melting point/K Low 302.93 High 1231

Formula of oxide E2O3 Ga2O3 EO2 GeO2

Formula of chloride E Cl3 GaCl3 ECl4 GeCl4

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 Classification of Elements and Periodicity in Properties 77
PERIODIC SYSTEM OF THE ELEMENTS IN GROUPS AND SERIES

Mendeleev’s Periodic Table published earlier

Fig. 3.1

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 78 chemistry

3.3 MODERN PERIODIC LAW AND THE physical and chemical properties of elements
PRESENT FORM OF THE PERIODIC and their compounds.
TABLE Numerous forms of Periodic Table have
We must bear in mind that when Mendeleev been devised from time to time. Some
developed his Periodic Table, chemists forms emphasise chemical reactions and
knew nothing about the internal structure valence, whereas others stress the electronic
of atom. However, the beginning of the 20th configuration of elements. A modern version,
century witnessed profound developments the so-called “long form” of the Periodic
in theories about sub-atomic particles. In Table of the elements (Fig. 3.2), is the most
1913, the English physicist, Henry Moseley convenient and widely used. The horizontal
observed regularities in the characteristic rows (which Mendeleev called series) are
X-ray spectra of the elements. A plot of called periods and the vertical columns,
(where is frequency of X-rays emitted) groups. Elements having similar outer
against atomic number (Z) gave a straight electronic configurations in their atoms
line and not the plot of vs atomic mass. are arranged in vertical columns, referred
He thereby showed that the atomic number to as groups or families. According to the
is a more fundamental property of an element recommendation of International Union of
Pure and Applied Chemistry (IUPAC), the
than its atomic mass. Mendeleev’s Periodic
groups are numbered from 1 to 18 replacing
Law was, therefore, accordingly modified. This
the older notation of groups IA … VIIA, VIII,
is known as the Modern Periodic Law and
IB … VIIB and 0.
can be stated as :
There are altogether seven periods. The
The physical and chemical properties period number corresponds to the highest
of the elements are periodic functions principal quantum number (n) of the elements
of their atomic numbers. in the period. The first period contains 2
The Periodic Law revealed important elements. The subsequent periods consists of
analogies among the 94 naturally occurring 8, 8, 18, 18 and 32 elements, respectively. The
elements (neptunium and plutonium like seventh period is incomplete and like the sixth
actinium and protoactinium are also found period would have a theoretical maximum
in pitch blende – an ore of uranium). It (on the basis of quantum numbers) of 32
stimulated renewed interest in Inorganic elements. In this form of the Periodic Table,
Chemistry and has carried into the present 14 elements of both sixth and seventh periods
with the creation of artificially produced (lanthanoids and actinoids, respectively) are
short-lived elements. placed in separate panels at the bottom*.
You may recall that the atomic number
3.4 NOMENCLATURE OF ELEMENTS
is equal to the nuclear charge (i.e., number
WITH ATOMIC NUMBERS > 100
of protons) or the number of electrons in
a neutral atom. It is then easy to visualize The naming of the new elements had been
the significance of quantum numbers and traditionally the privilege of the discoverer
electronic configurations in periodicity of (or discoverers) and the suggested name was
elements. In fact, it is now recognized that the ratified by the IUPAC. In recent years this has
Periodic Law is essentially the consequence led to some controversy. The new elements
of the periodic variation in electronic with very high atomic numbers are so unstable
configurations, which indeed determine the that only minute quantities, sometimes only

* Glenn T. Seaborg’s work in the middle of the 20th century starting with the discovery of plutonium in 1940, followed by
those of all the transuranium elements from 94 to 102 led to reconfiguration of the periodic table placing the actinoids below
the lanthanoids. In 1951, Seaborg was awarded the Nobel Prize in chemistry for his work. Element 106 has been named
Seaborgium (Sg) in his honour.

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Unit [Link] 79
0

IA IIA III B IV B VB VI B VII B

III A IV A VA VI A VII A ← VIII → IB II B

Classification of Elements and Periodicity in Properties

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Fig. 3.2 Long form of the Periodic Table of the Elements with their atomic numbers and ground state outer electronic
configurations. The groups are numbered 1-18 in accordance with the 1984 IUPAC recommendations. This
notation replaces the old numbering scheme of IA–VIIA, VIII, IB–VIIB and 0 for the elements.
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 80 chemistry

a few atoms of them are obtained. Their digits which make up the atomic number and
synthesis and characterisation, therefore, “ium” is added at the end. The IUPAC names
require highly sophisticated costly equipment for elements with Z above 100 are shown in
and laboratory. Such work is carried out with Table 3.5.
competitive spirit only in some laboratories
in the world. Scientists, before collecting the Table 3.4 Notation for IUPAC
reliable data on the new element, at times Nomenclature of Elements
get tempted to claim for its discovery. For
example, both American and Soviet scientists Digit Name Abbreviation
claimed credit for discovering element 104.
0 nil n
The Americans named it Rutherfordium
1 un u
whereas Soviets named it Kurchatovium. To
2 bi b
avoid such problems, the IUPAC has made
3 tri t
recommendation that until a new element’s
4 quad q
discovery is proved, and its name is officially
5 pent p
recognised, a systematic nomenclature be
6 hex h
derived directly from the atomic number of
7 sept s
the element using the numerical roots for
8 oct o
0 and numbers 1-9. These are shown in
9 enn e
Table 3.4. The roots are put together in order of

Table 3.5 Nomenclature of Elements with Atomic Number Above 100

Atomic Name according to IUPAC IUPAC

Symbol
Number IUPAC nomenclature Official Name Symbol

101 Unnilunium Unu Mendelevium Md

102 Unnilbium Unb Nobelium No
103 Unniltrium Unt Lawrencium Lr
104 Unnilquadium Unq Rutherfordium Rf
105 Unnilpentium Unp Dubnium Db
106 Unnilhexium Unh Seaborgium Sg
107 Unnilseptium Uns Bohrium Bh
108 Unniloctium Uno Hassium Hs
109 Unnilennium Une Meitnerium Mt
110 Ununnillium Uun Darmstadtium Ds
111 Unununnium Uuu Rontgenium Rg
112 Ununbium Uub Copernicium Cn
113 Ununtrium Uut Nihonium Nh
114 Ununquadium Uuq Flerovium Fl
115 Ununpentium Uup Moscovium Mc
116 Ununhexium Uuh Livermorium Lv
117 Ununseptium Uus Tennessine Ts
118 Ununoctium Uuo Oganesson Og

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 Classification of Elements and Periodicity in Properties 81

Thus, the new element first gets a be readily seen that the number of elements
temporary name, with symbol consisting in each period is twice the number of atomic
of three letters. Later permanent name orbitals available in the energy level that is
and symbol are given by a vote of IUPAC being filled. The first period (n = 1) starts with
representatives from each country. The the filling of the lowest level (1s) and therefore
permanent name might reflect the country has two elements — hydrogen (ls1) and helium
(or state of the country) in which the element (ls2) when the first shell (K) is completed. The
was discovered, or pay tribute to a notable second period (n = 2) starts with lithium and the
scientist. As of now, elements with atomic third electron enters the 2s orbital. The next
numbers up to 118 have been discovered. element, beryllium has four electrons and has
Official names of all elements have been the electronic configuration 1s22s2. Starting
announced by IUPAC. from the next element boron, the 2p orbitals
are filled with electrons when the L shell is
Problem 3.1 completed at neon (2s22p6). Thus there are
What would be the IUPAC name and 8 elements in the second period. The third
symbol for the element with atomic period (n = 3) begins at sodium, and the added
number 120? electron enters a 3s orbital. Successive filling
of 3s and 3p orbitals gives rise to the third
Solution period of 8 elements from sodium to argon. The
From Table 3.4, the roots for 1, 2 and 0 fourth period (n = 4) starts at potassium, and
are un, bi and nil, respectively. Hence, the added electrons fill up the 4s orbital. Now
the symbol and the name respectively you may note that before the 4p orbital is filled,
are Ubn and unbinilium. filling up of 3d orbitals becomes energetically
favourable and we come across the so called 3d
3.5 ELECTRONIC CONFIGURATIONS transition series of elements. This starts from
OF ELEMENTS AND THE PERIODIC scandium (Z = 21) which has the electronic
TABLE configuration 3d1 4s2. The 3d orbitals are filled
In the preceding unit we have learnt that an at zinc (Z=30) with electronic configuration
electron in an atom is characterised by a set 3d104s2. The fourth period ends at krypton
of four quantum numbers, and the principal with the filling up of the 4p orbitals. Altogether
quantum number (n ) defines the main energy we have 18 elements in this fourth period. The
level known as shell. We have also studied fifth period (n = 5) beginning with rubidium
about the filling of electrons into different is similar to the fourth period and contains
subshells, also referred to as orbitals (s, p, the 4d transition series starting at yttrium
d, f ) in an atom. The distribution of electrons (Z = 39). This period ends at xenon with the
into orbitals of an atom is called its electronic filling up of the 5p orbitals. The sixth period
configuration. An element’s location in the (n = 6) contains 32 elements and successive
Periodic Table reflects the quantum numbers electrons enter 6s, 4f, 5d and 6p orbitals, in
of the last orbital filled. In this section we the order — filling up of the 4f orbitals begins
will observe a direct connection between the with cerium (Z = 58) and ends at lutetium
electronic configurations of the elements and (Z = 71) to give the 4f-inner transition series
the long form of the Periodic Table. which is called the lanthanoid series. The
seventh period (n = 7) is similar to the sixth
(a) Electronic Configurations in Periods period with the successive filling up of the
The period indicates the value of n for the 7s, 5f, 6d and 7p orbitals and includes most
outermost or valence shell. In other words, of the man-made radioactive elements. This
successive period in the Periodic Table is period will end at the element with atomic
associated with the filling of the next higher number 118 which would belong to the noble
principal energy level (n = 1, n = 2, etc.). It can gas family. Filling up of the 5f orbitals after

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 82 chemistry

actinium (Z = 89) gives the 5f-inner transition a theoretical foundation for the periodic
series known as the actinoid series. The 4f- classification. The elements in a vertical column
and 5f-inner transition series of elements of the Periodic Table constitute a group or
are placed separately in the Periodic Table family and exhibit similar chemical behaviour.
to maintain its structure and to preserve the This similarity arises because these elements
principle of classification by keeping elements have the same number and same distribution
with similar properties in a single column. of electrons in their outermost orbitals. We
can classify the elements into four blocks viz.,
Problem 3.2 s-block, p-block, d-block and f-block
How would you justify the presence depending on the type of atomic orbitals that
of 18 elements in the 5th period of the are being filled with electrons. This is illustrated
Periodic Table? in Fig. 3.3. We notice two exceptions to this
Solution categorisation. Strictly, helium belongs to the
s-block but its positioning in the p-block
When n = 5, l = 0, 1, 2, 3. The order
in which the energy of the available along with other group 18 elements is
orbitals 4d, 5s and 5p increases is 5s justified because it has a completely filled
< 4d < 5p. The total number of orbitals valence shell (1s2) and as a result, exhibits
available are 9. The maximum number properties characteristic of other noble gases.
of electrons that can be accommodated The other exception is hydrogen. It has only
is 18; and therefore 18 elements are one s-electron and hence can be placed in
there in the 5th period. group 1 (alkali metals). It can also
gain an electron to achieve a noble gas
(b) Groupwise Electronic Configurations arrangement and hence it can behave
Elements in the same vertical column or similar to a group 17 (halogen family)
group have similar valence shell electronic elements. Because it is a special case, we
configurations, the same number of electrons shall place hydrogen separately at the top of
in the outer orbitals, and similar properties. the Periodic Table as shown in Fig. 3.2 and
For example, the Group 1 elements (alkali Fig. 3.3. We will briefly discuss the salient
metals) all have ns1 valence shell electronic features of the four types of elements marked in
configuration as shown below. the Periodic Table. More about these elements
Atomic number Symbol Electronic configuration
3 Li 1s22s1 (or) [He]2s1
11 Na 1s22s22p63s1 (or) [Ne]3s1
19 K 1s22s22p63s23p64s1 (or) [Ar]4s1
37 Rb 1s22s22p63s23p63d104s24p65s1 (or) [Kr]5s1
55 Cs 1s22s22p63s23p63d104s24p64d105s25p66s1 (or) [Xe]6s1
87 Fr [Rn]7s1

Thus it can be seen that the properties of will be discussed later. During the description
an element have periodic dependence upon of their features certain terminology has been
its atomic number and not on relative atomic used which has been classified in section 3.7.
mass.
3.6 ELECTRONIC CONFIGURATIONS 3.6.1 The s-Block Elements
AND TY P E S OF E L E M E NTS : The elements of Group 1 (alkali metals) and
s-, p-, d-, f- BLOCKS Group 2 (alkaline earth metals) which have
The aufbau (build up) principle and the ns1 and ns2 outermost electronic configuration
electronic configuration of atoms provide belong to the s-Block Elements. They are all

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Unit [Link] 83
Nh Mc Ts Og
Classification of Elements and Periodicity in Properties

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Fig. 3.3 The types of elements in the Periodic Table based on the orbitals that
are being filled. Also shown is the broad division of elements into METALS
( ), NON-METALS ( ) and METALLOIDS ( ).
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 84 chemistry

reactive metals with low ionization enthalpies. valence (oxidation states), paramagnetism and
They lose the outermost electron(s) readily to oftenly used as catalysts. However, Zn, Cd and
form 1+ ion (in the case of alkali metals) or 2+ Hg which have the electronic configuration,
ion (in the case of alkaline earth metals). The (n-1) d10ns2 do not show most of the properties
metallic character and the reactivity increase of transition elements. In a way, transition
as we go down the group. Because of high metals form a bridge between the chemically
reactivity they are never found pure in nature. active metals of s-block elements and the
The compounds of the s-block elements, with less active elements of Groups 13 and 14 and
the exception of those of lithium and beryllium thus take their familiar name “Transition
are predominantly ionic. Elements”.

3.6.2 The p-Block Elements 3.6.4 The f-Block Elements

(Inner-Transition Elements)
The p-Block Elements comprise those
belonging to Group 13 to 18 and these The two rows of elements at the bottom of
the Periodic Table, called the Lanthanoids,
together with the s-Block Elements are
Ce(Z = 58) – Lu(Z = 71) and Actinoids,
called the Representative Elements or Main Th(Z = 90) – Lr (Z = 103) are characterised by
Group Elements. The outermost electronic the outer electronic configuration (n-2)f1-14
configuration varies from ns2np1 to ns2np6 (n-1)d0–1ns2. The last electron added to each
in each period. At the end of each period is element is filled in f- orbital. These two series
a noble gas element with a closed valence of elements are hence called the Inner-
shell ns2np6 configuration. All the orbitals Transition Elements (f-Block Elements).
in the valence shell of the noble gases are They are all metals. Within each series, the
completely filled by electrons and it is very properties of the elements are quite similar.
difficult to alter this stable arrangement by The chemistry of the early actinoids is
the addition or removal of electrons. The more complicated than the corresponding
noble gases thus exhibit very low chemical lanthanoids, due to the large number of
reactivity. Preceding the noble gas family oxidation states possible for these actinoid
are two chemically important groups of non- elements. Actinoid elements are radioactive.
Many of the actinoid elements have been made
metals. They are the halogens (Group 17) and
only in nanogram quantities or even less by
the chalcogens (Group 16). These two groups
nuclear reactions and their chemistry is not
of elements have highly negative electron fully studied. The elements after uranium are
gain enthalpies and readily add one or two called Transuranium Elements.
electrons respectively to attain the stable
noble gas configuration. The non-metallic Problem 3.3
character increases as we move from left to
The elements Z = 117 and 120 have not yet
right across a period and metallic character been discovered. In which family/group
increases as we go down the group. would you place these elements and
also give the electronic configuration in
3.6.3 The d-Block Elements (Transition
each case.
Elements)
These are the elements of Group 3 to 12 in Solution
the centre of the Periodic Table. These are We see from Fig. 3.2, that element
characterised by the filling of inner d orbitals with Z = 117, would belong to the
by electrons and are therefore referred to as halogen family (Group 17) and the
d-Block Elements. These elements have electronic configuration would be [Rn]
5f146d107s27p5. The element with Z = 120,
the general outer electronic configuration
will be placed in Group 2 (alkaline earth
(n-1)d1-10ns0-2 except for Pd where its electronic metals), and will have the electronic
configuration is 4d105s0.. They are all metals. configuration [Uuo]8s2.
They mostly form coloured ions, exhibit variable

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 Classification of Elements and Periodicity in Properties 85

3.6.5 Metals, Non-metals and Metalloids

Solution
In addition to displaying the classification
of elements into s-, p-, d-, and f-blocks, Metallic character increases down a
group and decreases along a period as
Fig. 3.3 shows another broad classification
we move from left to right. Hence the
of elements based on their properties. The order of increasing metallic character
elements can be divided into Metals and is: P < Si < Be < Mg < Na.
Non-Metals. Metals comprise more than
78% of all known elements and appear on 3.7 PERIODIC TRENDS IN PROPERTIES
the left side of the Periodic Table. Metals are OF ELEMENTS
usually solids at room temperature [mercury
There are many observable patterns in the
is an exception; gallium and caesium also
physical and chemical properties of elements
have very low melting points (303K and
as we descend in a group or move across a
302K, respectively)]. Metals usually have high
period in the Periodic Table. For example,
melting and boiling points. They are good within a period, chemical reactivity tends to
conductors of heat and electricity. They are be high in Group 1 metals, lower in elements
malleable (can be flattened into thin sheets by towards the middle of the table, and increases
hammering) and ductile (can be drawn into to a maximum in the Group 17 non-metals.
wires). In contrast, non-metals are located at Likewise within a group of representative
the top right hand side of the Periodic Table. metals (say alkali metals) reactivity increases
In fact, in a horizontal row, the property of on moving down the group, whereas within a
elements change from metallic on the left to group of non-metals (say halogens), reactivity
non-metallic on the right. Non-metals are decreases down the group. But why do the
usually solids or gases at room temperature properties of elements follow these trends?
with low melting and boiling points (boron And how can we explain periodicity? To
and carbon are exceptions). They are poor answer these questions, we must look into the
conductors of heat and electricity. Most non- theories of atomic structure and properties
metallic solids are brittle and are neither of the atom. In this section we shall discuss
malleable nor ductile. The elements become the periodic trends in certain physical and
more metallic as we go down a group; the chemical properties and try to explain them
non-metallic character increases as one goes in terms of number of electrons and energy
from left to right across the Periodic Table. levels.
The change from metallic to non-metallic
3.7.1 Trends in Physical Properties
character is not abrupt as shown by the thick
zig-zag line in Fig. 3.3. The elements (e.g., There are numerous physical properties of
silicon, germanium, arsenic, antimony and elements such as melting and boiling points,
tellurium) bordering this line and running heats of fusion and vaporization, energy
diagonally across the Periodic Table show of atomization, etc. which show periodic
variations. However, we shall discuss the
properties that are characteristic of both
periodic trends with respect to atomic and
metals and non-metals. These elements are
ionic radii, ionization enthalpy, electron gain
called Semi-metals or Metalloids.
enthalpy and electronegativity.
Problem 3.4 (a) Atomic Radius
Considering the atomic number and You can very well imagine that finding the
position in the periodic table, arrange size of an atom is a lot more complicated than
the following elements in the increasing
measuring the radius of a ball. Do you know
order of metallic character : Si, Be, Mg,
Na, P. why? Firstly, because the size of an atom
(~ 1.2 Å i.e., 1.2 × 10–10 m in radius) is very

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 86 chemistry

small. Secondly, since the electron cloud The atomic radii of a few elements are listed
surrounding the atom does not have a sharp in Table 3.6. Two trends are obvious. We can
boundary, the determination of the atomic explain these trends in terms of nuclear charge
size cannot be precise. In other words, there and energy level. The atomic size generally
is no practical way by which the size of an decreases across a period as illustrated in
individual atom can be measured. However, Fig. 3.4(a) for the elements of the second
an estimate of the atomic size can be made by period. It is because within the period the
knowing the distance between the atoms in outer electrons are in the same valence shell
the combined state. One practical approach to and the effective nuclear charge increases
estimate the size of an atom of a non-metallic as the atomic number increases resulting in
element is to measure the distance between the increased attraction of electrons to the
two atoms when they are bound together nucleus. Within a family or vertical column
by a single bond in a covalent molecule and of the periodic table, the atomic radius
from this value, the “Covalent Radius” of the increases regularly with atomic number as
element can be calculated. For example, the illustrated in Fig. 3.4(b). For alkali metals
bond distance in the chlorine molecule (Cl2) and halogens, as we descend the groups,
is 198 pm and half this distance (99 pm), is the principal quantum number (n) increases
taken as the atomic radius of chlorine. For
and the valence electrons are farther from
metals, we define the term “Metallic Radius”
the nucleus. This happens because the inner
which is taken as half the internuclear
energy levels are filled with electrons, which
distance separating the metal cores in the
serve to shield the outer electrons from the
metallic crystal. For example, the distance
pull of the nucleus. Consequently the size of
between two adjacent copper atoms in solid
copper is 256 pm; hence the metallic radius the atom increases as reflected in the atomic
of copper is assigned a value of 128 pm. For radii.
simplicity, in this book, we use the term Note that the atomic radii of noble gases
Atomic Radius to refer to both covalent or are not considered here. Being monoatomic,
metallic radius depending on whether the their (non-bonded radii) values are very
element is a non-metal or a metal. Atomic large. In fact radii of noble gases should be
radii can be measured by X-ray or other compared not with the covalent radii but with
spectroscopic methods. the van der Waals radii of other elements.

Table 3.6(a) Atomic Radii/pm Across the Periods

Atom (Period II) Li Be B C N O F
Atomic radius 152 111 88 77 74 66 64
Atom (Period III) Na Mg Al Si P S Cl
Atomic radius 186 160 143 117 110 104 99

Table 3.6(b) Atomic Radii/pm Down a Family

Atom Atomic Atom Atomic
(Group I) Radius (Group 17) Radius
Li 152 F 64
Na 186 Cl 99
K 231 Br 114
Rb 244 I 133
Cs 262 At 140

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 Classification of Elements and Periodicity in Properties 87

Fig. 3.4 (a) Variation of atomic radius with atomic Fig. 3.4 (b) Variation of atomic radius with
number across the second period atomic number for alkali metals and
halogens

(b) Ionic Radius cation with the greater positive charge will
The removal of an electron from an atom have a smaller radius because of the greater
results in the formation of a cation, whereas attraction of the electrons to the nucleus.
gain of an electron leads to an anion. The Anion with the greater negative charge will
ionic radii can be estimated by measuring have the larger radius. In this case, the net
the distances between cations and anions repulsion of the electrons will outweigh the
in ionic crystals. In general, the ionic radii nuclear charge and the ion will expand in size.
of elements exhibit the same trend as the
atomic radii. A cation is smaller than its Problem 3.5
parent atom because it has fewer electrons Which of the following species will have
while its nuclear charge remains the same. the largest and the smallest size?
The size of an anion will be larger than that of Mg, Mg2+, Al, Al3+.
the parent atom because the addition of one Solution
or more electrons would result in increased
Atomic radii decrease across a period.
repulsion among the electrons and a decrease Cations are smaller than their parent
in effective nuclear charge. For example, the atoms. Among isoelectronic species,
ionic radius of fluoride ion (F–) is 136 pm the one with the larger positive nuclear
whereas the atomic radius of fluorine is only charge will have a smaller radius.
64 pm. On the other hand, the atomic radius Hence the largest species is Mg; the
of sodium is 186 pm compared to the ionic smallest one is Al3+.
radius of 95 pm for Na+.
When we find some atoms and ions which (c) Ionization Enthalpy
contain the same number of electrons, we call A quantitative measure of the tendency of
them isoelectronic species*. For example, an element to lose electron is given by its
O2–, F–, Na+ and Mg2+ have the same number Ionization Enthalpy. It represents the
of electrons (10). Their radii would be different energy required to remove an electron from an
because of their different nuclear charges. The isolated gaseous atom (X) in its ground state.

* Two or more species with same number of atoms, same number of valence electrons and same structure, regardless of the
nature of elements involved.

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In other words, the first ionization enthalpy

for an element X is the enthalpy change
(∆i H) for the reaction depicted in equation 3.1.
X(g) → X+(g) + e– (3.1)
The ionization enthalpy is expressed in
units of kJ mol–1. We can define the second
ionization enthalpy as the energy required
to remove the second most loosely bound
electron; it is the energy required to carry out
the reaction shown in equation 3.2.
X+(g) → X2+(g) + e– (3.2)
Energy is always required to remove
electrons from an atom and hence ionization Fig. 3.5 Variation of first ionization enthalpies
(∆iH) with atomic number for elements
enthalpies are always positive. The second
with Z = 1 to 60
ionization enthalpy will be higher than the
first ionization enthalpy because it is more can be correlated with their high reactivity.
difficult to remove an electron from a positively In addition, you will notice two trends the
charged ion than from a neutral atom. In the first ionization enthalpy generally increases
same way the third ionization enthalpy will be as we go across a period and decreases
higher than the second and so on. The term as we descend in a group. These trends
“ionization enthalpy”, if not qualified, is taken are illustrated in Figs. 3.6(a) and 3.6(b)
as the first ionization enthalpy. respectively for the elements of the second
The first ionization enthalpies of elements period and the first group of the periodic
having atomic numbers up to 60 are plotted table. You will appreciate that the ionization
in Fig. 3.5. The periodicity of the graph is enthalpy and atomic radius are closely related
quite striking. You will find maxima at the properties. To understand these trends, we
noble gases which have closed electron shells have to consider two factors : (i) the attraction
and very stable electron configurations. On of electrons towards the nucleus, and (ii) the
the other hand, minima occur at the alkali repulsion of electrons from each other. The
metals and their low ionization enthalpies effective nuclear charge experienced by a

3.6 (a) 3.6 (b)

Fig. 3.6(a) F i r s t i o n i z a t i o n e n t h a l p i e s ( ∆ i H ) o f e l e m e n t s o f t h e s e c o n d p e r i o d a s a
function of atomic number (Z) and Fig. 3.6(b) ∆iH of alkali metals as a function of Z.

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 Classification of Elements and Periodicity in Properties 89

valence electron in an atom will be less than the 2s electrons of beryllium. Therefore, it is
the actual charge on the nucleus because of easier to remove the 2p-electron from boron
“shielding” or “screening” of the valence compared to the removal of a 2s- electron from
electron from the nucleus by the intervening beryllium. Thus, boron has a smaller first
core electrons. For example, the 2s electron ionization enthalpy than beryllium. Another
in lithium is shielded from the nucleus by “anomaly” is the smaller first ionization
the inner core of 1s electrons. As a result, the enthalpy of oxygen compared to nitrogen. This
valence electron experiences a net positive arises because in the nitrogen atom, three
charge which is less than the actual charge 2p-electrons reside in different atomic orbitals
of +3. In general, shielding is effective when (Hund’s rule) whereas in the oxygen atom,
the orbitals in the inner shells are completely two of the four 2p-electrons must occupy the
filled. This situation occurs in the case of same 2p-orbital resulting in an increased
alkali metals which have single outermost electron-electron repulsion. Consequently,
ns-electron preceded by a noble gas electronic it is easier to remove the fourth 2p-electron
configuration. from oxygen than it is, to remove one of the
When we move from lithium to fluorine three 2p-electrons from nitrogen.
across the second period, successive electrons
are added to orbitals in the same principal Problem 3.6
quantum level and the shielding of the nuclear The first ionization enthalpy (∆i H ) values
charge by the inner core of electrons does of the third period elements, Na, Mg and
not increase very much to compensate for Si are respectively 496, 737 and 786 kJ
the increased attraction of the electron to the mol–1. Predict whether the first ∆i H value
nucleus. Thus, across a period, increasing for Al will be more close to 575 or 760 kJ
nuclear charge outweighs the shielding. mol–1 ? Justify your answer.
Consequently, the outermost electrons are Solution
held more and more tightly and the ionization
It will be more close to 575 kJ mol–1.
enthalpy increases across a period. As we go
The value for Al should be lower than
down a group, the outermost electron being
that of Mg because of effective shielding
increasingly farther from the nucleus, there is of 3p electrons from the nucleus by
an increased shielding of the nuclear charge 3s-electrons.
by the electrons in the inner levels. In this
case, increase in shielding outweighs the (d) Electron Gain Enthalpy
increasing nuclear charge and the removal of
When an electron is added to a neutral
the outermost electron requires less energy
gaseous atom (X) to convert it into a negative
down a group.
ion, the enthalpy change accompanying the
From Fig. 3.6(a), you will also notice that process is defined as the Electron Gain
the first ionization enthalpy of boron (Z = 5) Enthalpy (∆ egH). Electron gain enthalpy
is slightly less than that of beryllium (Z = 4) provides a measure of the ease with which
even though the former has a greater nuclear an atom adds an electron to form anion as
charge. When we consider the same principal represented by equation 3.3.
quantum level, an s-electron is attracted to the
nucleus more than a p-electron. In beryllium, X(g) + e – → X –(g) (3.3)
the electron removed during the ionization is Depending on the element, the process
an s-electron whereas the electron removed of adding an electron to the atom can be
during ionization of boron is a p-electron. The either endothermic or exothermic. For many
penetration of a 2s-electron to the nucleus is elements energy is released when an electron
more than that of a 2p-electron; hence the 2p is added to the atom and the electron gain
electron of boron is more shielded from the enthalpy is negative. For example, group
nucleus by the inner core of electrons than 17 elements (the halogens) have very high

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Table 3.7 Electron Gain Enthalpies* / (kJ mol–1) of Some Main Group Elements

Group 1 ∆egH Group 16 ∆egH Group 17 ∆egH Group 0 ∆egH

H – 73 He + 48
Li – 60 O – 141 F – 328 Ne + 116
Na – 53 S – 200 Cl – 349 Ar + 96
K – 48 Se – 195 Br – 325 Kr + 96
Rb – 47 Te – 190 I – 295 Xe + 77
Cs – 46 Po – 174 At – 270 Rn + 68

negative electron gain enthalpies because

they can attain stable noble gas electronic Problem 3.7
configurations by picking up an electron. Which of the following will have the most
On the other hand, noble gases have large negative electron gain enthalpy and
positive electron gain enthalpies because the which the least negative?
electron has to enter the next higher principal P, S, Cl, F.
quantum level leading to a very unstable Explain your answer.
electronic configuration. It may be noted that Solution
electron gain enthalpies have large negative
values toward the upper right of the periodic Electron gain enthalpy generally
table preceding the noble gases. becomes more negative across a
period as we move from left to right.
The variation in electron gain enthalpies of Within a group, electron gain enthalpy
elements is less systematic than for ionization becomes less negative down a group.
enthalpies. As a general rule, electron gain However, adding an electron to the
enthalpy becomes more negative with increase 2p-orbital leads to greater repulsion
in the atomic number across a period. The than adding an electron to the larger
effective nuclear charge increases from left to 3p-orbital. Hence the element with
right across a period and consequently it will most negative electron gain enthalpy is
be easier to add an electron to a smaller atom chlorine; the one with the least negative
since the added electron on an average would electron gain enthalpy is phosphorus.
be closer to the positively charged nucleus. We
should also expect electron gain enthalpy to (e) Electronegativity
become less negative as we go down a group
A qualitative measure of the ability of an atom
because the size of the atom increases and
the added electron would be farther from the in a chemical compound to attract shared
nucleus. This is generally the case (Table electrons to itself is called electronegativity.
3.7). However, electron gain enthalpy of O or Unlike ionization enthalpy and electron gain
F is less negative than that of the succeeding enthalpy, it is not a measureable quantity.
element. This is because when an electron is However, a number of numerical scales of
added to O or F, the added electron goes to electronegativity of elements viz., Pauling
the smaller n = 2 quantum level and suffers scale, Mulliken-Jaffe scale, Allred-Rochow
significant repulsion from the other electrons scale have been developed. The one which
present in this level. For the n = 3 quantum is the most widely used is the Pauling scale.
level (S or Cl), the added electron occupies Linus Pauling, an American scientist, in 1922
a larger region of space and the electron- assigned arbitrarily a value of 4.0 to fluorine,
electron repulsion is much less. the element considered to have the greatest
* In many books, the negative of the enthalpy change for the process depicted in equation 3.3 is defined as the ELECTRON
AFFINITY (Ae ) of the atom under consideration. If energy is released when an electron is added to an atom, the electron
affinity is taken as positive, contrary to thermodynamic convention. If energy has to be supplied to add an electron to an
atom, then the electron affinity of the atom is assigned a negative sign. However, electron affinity is defined as absolute
zero and, therefore at any other temperature (T) heat capacities of the reactants and the products have to be taken into
account in ∆egH = –Ae – 5/2 RT.

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 Classification of Elements and Periodicity in Properties 91

ability to attract electrons. Approximate On the same account electronegativity values

values for the electronegativity of a few decrease with the increase in atomic radii
elements are given in Table 3.8(a) down a group. The trend is similar to that of
ionization enthalpy.
The electronegativity of any given element
is not constant; it varies depending on the Knowing the relationship between
element to which it is bound. Though it is electronegativity and atomic radius, can
not a measurable quantity, it does provide a you now visualise the relationship between
means of predicting the nature of force that electronegativity and non-metallic properties?
holds a pair of atoms together – a relationship Non-metallic elements have strong tendency
that you will explore later.
Electronegativity generally
increases across a period from
left to right (say from lithium to
fluorine) and decrease down a group
(say from fluorine to astatine)
in the periodic table. How can
these trends be explained?
Can the electronegativity be
related to atomic radii, which
tend to decrease across each
period from left to right, but
increase down each group ? The
attraction between the outer
(or valence) electrons and the
nucleus increases as the atomic
radius decreases in a period. The
electronegativity also increases.
Fig. 3.7 The periodic trends of elements in the periodic table

Table 3.8(a) Electronegativity Values (on Pauling scale) Across the Periods
Atom (Period II) Li Be B C N O F

Electronegativity 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Atom (Period III) Na Mg Al Si P S Cl

Electronegativity 0.9 1.2 1.5 1.8 2.1 2.5 3.0

Table 3.8(b) Electronegativity Values (on Pauling scale) Down a Family

Atom Electronegativity Atom Electronegativity

(Group I) Value (Group 17) Value
Li 1.0 F 4.0
Na 0.9 Cl 3.0
K 0.8 Br 2.8
Rb 0.8 I 2.5
Cs 0.7 At 2.2

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to gain electrons. Therefore, electronegativity is with outer electronic configuration 2s22p5,

directly related to that non-metallic properties shares one electron with oxygen in the OF2
of elements. It can be further extended to say molecule. Being highest electronegative
that the electronegativity is inversely related element, fluorine is given oxidation state
to the metallic properties of elements. Thus, –1. Since there are two fluorine atoms in
the increase in electronegativities across this molecule, oxygen with outer electronic
a period is accompanied by an increase configuration 2s22p4 shares two electrons
in non-metallic properties (or decrease in with fluorine atoms and thereby exhibits
metallic properties) of elements. Similarly, the oxidation state +2. In Na2O, oxygen being
decrease in electronegativity down a group is more electronegative accepts two electrons,
accompanied by a decrease in non-metallic one from each of the two sodium atoms and,
properties (or increase in metallic properties) thus, shows oxidation state –2. On the other
of elements. hand sodium with electronic configuration
All these periodic trends are summarised 3s1 loses one electron to oxygen and is given
in Figure 3.7. oxidation state +1. Thus, the oxidation state
of an element in a particular compound can
3.7.2 Periodic Trends in Chemical be defined as the charge acquired by its atom
Properties on the basis of electronegative consideration
Most of the trends in chemical properties of from other atoms in the molecule.
elements, such as diagonal relationships, inert
pair effect, effects of lanthanoid contraction Problem 3.8
etc. will be dealt with along the discussion Using the Periodic Table, predict the
of each group in later units. In this section formulas of compounds which might
we shall study the periodicity of the valence be formed by the following pairs of
state shown by elements and the anomalous elements; (a) silicon and bromine
properties of the second period elements (from (b) aluminium and sulphur.
lithium to fluorine).
Solution
(a) Periodicity of Valence or Oxidation (a) Silicon is group 14 element with
States a valence of 4; bromine belongs to
The valence is the most characteristic property the halogen family with a valence
of the elements and can be understood in of 1. Hence the formula of the
compound formed would be SiBr4.
terms of their electronic configurations. The
valence of representative elements is usually (b) Aluminium belongs to group
(though not necessarily) equal to the number 13 with a valence of 3; sulphur
belongs to group 16 elements with
of electrons in the outermost orbitals and/or
a valence of 2. Hence, the formula
equal to eight minus the number of outermost
of the compound formed would be
electrons as shown below. Al2S3.
Nowadays the term oxidation state is
frequently used for valence. Consider the Some periodic trends observed in the
two oxygen containing compounds: OF2 and valence of elements (hydrides and oxides)
Na2O. The order of electronegativity of the are shown in Table 3.9. Other such periodic
three elements involved in these compounds trends which occur in the chemical behaviour
is F > O > Na. Each of the atoms of fluorine, of the elements are discussed elsewhere in

Group 1 2 13 14 15 16 17 18
Number of valence 1 2 3 4 5 6 7 8
electron
alence 1 2 3 4 3,5 2,6 1,7 0,8

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 Classification of Elements and Periodicity in Properties 93

Table 3.9 Periodic Trends in Valence of Elements as shown by the Formulas of Their
Compounds
Group 1 2 13 14 15 16 17

Formula of LiH CaH2 B2H6 CH4 NH3 H2O HF

hydride NaH AlH3 SiH4 PH3 H2S HCl
KH GeH4 AsH3 H2Se HBr
SnH4 H2Te HI

Formula Li2O MgO B2O3 CO2 N2O3, N2O5 –

of oxide Na2O CaO Al2O3 SiO2 P4O6, P4O10 SO3 Cl2 O7
K2O SrO Ga2O3 GeO2 As2O3, As2O5 SeO3 –
BaO In2O3 SnO2 Sb2O3, Sb2O5 TeO3 –
PbO2 Bi2O3 – –

this book. There are many elements which the second element of the following group
exhibit variable valence. This is particularly i.e., magnesium and aluminium, respectively.
characteristic of transition elements and This sort of similarity is commonly referred
actinoids, which we shall study later. to as diagonal relationship in the periodic
properties.
(b) Anomalous Properties of Second
Period Elements What are the reasons for the different
chemical behaviour of the first member of
The first element of each of the groups 1
a group of elements in the s- and p-blocks
(lithium) and 2 (beryllium) and groups 13-17
compared to that of the subsequent members
(boron to fluorine) differs in many respects
in the same group? The anomalous behaviour
from the other members of their respective
is attributed to their small size, large charge/
group. For example, lithium unlike other
radius ratio and high electronegativity of the
alkali metals, and beryllium unlike other
elements. In addition, the first member of
alkaline earth metals, form compounds with
group has only four valence orbitals (2s and
pronounced covalent character; the other
2p) available for bonding, whereas the second
members of these groups predominantly member of the groups have nine valence
form ionic compounds. In fact the behaviour orbitals (3s, 3p, 3d). As a consequence of
of lithium and beryllium is more similar with this, the maximum covalency of the first
member of each group is 4 (e.g., boron
Property Element
can only form  BF4  , whereas the other


members of the groups can expand their

Metallic radius M/pm Li Be B valence shell to accommodate more than
152 111 88 four pairs of electrons e.g., aluminium
Na Mg Al
 AlF 
3
6
forms). Furthermore, the first
186 160 143 member of p-block elements displays
greater ability to form pπ – pπ multiple
Ionic radius M+/pm Li Be bonds to itself (e.g., C = C, C ≡ C,
76 31 N = N, N ≡ Ν) and to other second period
Na Mg elements (e.g., C = O, C = N, C ≡ N,
102 72 N = O) compared to subsequent members
of the same group.

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 94 chemistry

here it can be directly related to the metallic

Problem 3.9 and non-metallic character of elements. Thus,
Are the oxidation state and covalency of the metallic character of an element, which
Al in [AlCl(H2O)5]2+ same ? is highest at the extremely left decreases and
Solution the non-metallic character increases while
No. The oxidation state of Al is +3 and moving from left to right across the period.
the covalency is 6. The chemical reactivity of an element can be
best shown by its reactions with oxygen and
3.7.3 Periodic Trends and Chemical halogens. Here, we shall consider the reaction
Reactivity of the elements with oxygen only. Elements
We have observed the periodic trends in on two extremes of a period easily combine
certain fundamental properties such as with oxygen to form oxides. The normal oxide
atomic and ionic radii, ionization enthalpy, formed by the element on extreme left is the
electron gain enthalpy and valence. We most basic (e.g., Na2O), whereas that formed
know by now that the periodicity is related to by the element on extreme right is the most
electronic configuration. That is, all chemical acidic (e.g., Cl2O7). Oxides of elements in the
and physical properties are a manifestation of centre are amphoteric (e.g., Al2O3, As2O3) or
the electronic configuration of elements. We neutral (e.g., CO, NO, N2O). Amphoteric oxides
shall now try to explore relationships between behave as acidic with bases and as basic with
these fundamental properties of elements with acids, whereas neutral oxides have no acidic
their chemical reactivity. or basic properties.
The atomic and ionic radii, as we know,
generally decrease in a period from left to right. Problem 3.10
As a consequence, the ionization enthalpies Show by a chemical reaction with water
generally increase (with some exceptions as that Na2O is a basic oxide and Cl2O7 is
an acidic oxide.
outlined in section 3.7.1(a)) and electron gain
enthalpies become more negative across a Solution
period. In other words, the ionization enthalpy Na2O with water forms a strong base
of the extreme left element in a period is the whereas Cl2O7 forms strong acid.
least and the electron gain enthalpy of the Na2O + H2O → 2NaOH
element on the extreme right is the highest Cl2O7 + H2O → 2HClO4
negative (note : noble gases having completely
filled shells have rather positive electron Their basic or acidic nature can be
gain enthalpy values). This results into high qualitatively tested with litmus paper.
chemical reactivity at the two extremes and
the lowest in the centre. Thus, the maximum Among transition metals (3d series), the
chemical reactivity at the extreme left (among change in atomic radii is much smaller as
alkali metals) is exhibited by the loss of an compared to those of representative elements
electron leading to the formation of a cation across the period. The change in atomic radii
and at the extreme right (among halogens) is still smaller among inner-transition metals
shown by the gain of an electron forming (4f series). The ionization enthalpies are
an anion. This property can be related with intermediate between those of s- and p-blocks.
the reducing and oxidizing behaviour of the As a consequence, they are less electropositive
elements which you will learn later. However, than group 1 and 2 metals.

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 Classification of Elements and Periodicity in Properties 95

In a group, the increase in atomic and increases down the group and non-metallic
ionic radii with increase in atomic number character decreases. This trend can be related
generally results in a gradual decrease in with their reducing and oxidizing property
ionization enthalpies and a regular decrease which you will learn later. In the case of
(with exception in some third period elements transition elements, however, a reverse trend
as shown in section 3.7.1(d)) in electron is observed. This can be explained in terms of
gain enthalpies in the case of main group atomic size and ionization enthalpy.
elements. Thus, the metallic character

SUMMARY

In this Unit, you have studied the development of the Periodic Law and the Periodic Table.
Mendeleev’s Periodic Table was based on atomic masses. Modern Periodic Table arranges
the elements in the order of their atomic numbers in seven horizontal rows (periods) and
eighteen vertical columns (groups or families). Atomic numbers in a period are consecutive,
whereas in a group they increase in a pattern. Elements of the same group have similar
valence shell electronic configuration and, therefore, exhibit similar chemical properties.
However, the elements of the same period have incrementally increasing number of electrons
from left to right, and, therefore, have different valencies. Four types of elements can be
recognized in the periodic table on the basis of their electronic configurations. These are
s-block, p-block, d-block and f-block elements. Hydrogen with one electron in the 1s orbital
occupies a unique position in the periodic table. Metals comprise more than seventy eight
per cent of the known elements. Non-metals, which are located at the top of the periodic
table, are less than twenty in number. Elements which lie at the border line between metals
and non-metals (e.g., Si, Ge, As) are called metalloids or semi-metals. Metallic character
increases with increasing atomic number in a group whereas decreases from left to right
in a period. The physical and chemical properties of elements vary periodically with their
atomic numbers.

Periodic trends are observed in atomic sizes, ionization enthalpies, electron gain
enthalpies, electronegativity and valence. The atomic radii decrease while going from
left to right in a period and increase with atomic number in a group. Ionization enthalpies
generally increase across a period and decrease down a group. Electronegativity also shows
a similar trend. Electron gain enthalpies, in general, become more negative across a period
and less negative down a group. There is some periodicity in valence, for example, among
representative elements, the valence is either equal to the number of electrons in the
outermost orbitals or eight minus this number. Chemical reactivity is highest at the two
extremes of a period and is lowest in the centre. The reactivity on the left extreme of a period
is because of the ease of electron loss (or low ionization enthalpy). Highly reactive elements
do not occur in nature in free state; they usually occur in the combined form. Oxides formed
of the elements on the left are basic and of the elements on the right are acidic in nature.
Oxides of elements in the centre are amphoteric or neutral.

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 96 chemistry

Exercises

3.1 What is the basic theme of organisation in the periodic table?

3.2 Which important property did Mendeleev use to classify the elements in his periodic
table and did he stick to that?
3.3 What is the basic difference in approach between the Mendeleev’s Periodic Law and
the Modern Periodic Law?
3.4 On the basis of quantum numbers, justify that the sixth period of the periodic table
should have 32 elements.
3.5 In terms of period and group where would you locate the element with Z =114?
3.6 Write the atomic number of the element present in the third period and seventeenth
group of the periodic table.
3.7 Which element do you think would have been named by
(i) Lawrence Berkeley Laboratory
(ii) Seaborg’s group?
3.8 Why do elements in the same group have similar physical and chemical properties?
3.9 What does atomic radius and ionic radius really mean to you?
3.10 How do atomic radius vary in a period and in a group? How do you explain the
variation?
3.11 What do you understand by isoelectronic species? Name a species that will be
isoelectronic with each of the following atoms or ions.
(i) F– (ii) Ar (iii) Mg2+ (iv) Rb+
3.12 Consider the following species :
N3–, O2–, F–, Na+, Mg2+ and Al3+
(a) What is common in them?
(b) Arrange them in the order of increasing ionic radii.
3.13 Explain why cation are smaller and anions larger in radii than their parent atoms?
3.14 What is the significance of the terms — ‘isolated gaseous atom’ and ‘ground state’
while defining the ionization enthalpy and electron gain enthalpy?
Hint : Requirements for comparison purposes.
3.15 Energy of an electron in the ground state of the hydrogen atom is
–2.18×10–18J. Calculate the ionization enthalpy of atomic hydrogen in terms of
J mol–1.
Hint: Apply the idea of mole concept to derive the answer.
3.16 Among the second period elements the actual ionization enthalpies are in the order
Li < B < Be < C < O < N < F < Ne.
Explain why
(i) Be has higher ∆i H than B
(ii) O has lower ∆i H than N and F?

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 Classification of Elements and Periodicity in Properties 97

3.17 How would you explain the fact that the first ionization enthalpy of sodium is lower
than that of magnesium but its second ionization enthalpy is higher than that of
magnesium?
3.18 What are the various factors due to which the ionization enthalpy of the main group
elements tends to decrease down a group?
3.19 The first ionization enthalpy values (in kJ mol–1) of group 13 elements are :
B Al Ga In Tl
801 577 579 558 589
How would you explain this deviation from the general trend ?
3.20 Which of the following pairs of elements would have a more negative electron gain
enthalpy?
(i) O or F (ii) F or Cl
3.21 Would you expect the second electron gain enthalpy of O as positive, more negative
or less negative than the first? Justify your answer.
3.22 What is the basic difference between the terms electron gain enthalpy and
electronegativity?
3.23 How would you react to the statement that the electronegativity of N on Pauling
scale is 3.0 in all the nitrogen compounds?
3.24 Describe the theory associated with the radius of an atom as it
(a) gains an electron
(b) loses an electron
3.25 Would you expect the first ionization enthalpies for two isotopes of the same element
to be the same or different? Justify your answer.
3.26 What are the major differences between metals and non-metals?
3.27 Use the periodic table to answer the following questions.
(a) Identify an element with five electrons in the outer subshell.
(b) Identify an element that would tend to lose two electrons.
(c) Identify an element that would tend to gain two electrons.
(d) Identify the group having metal, non-metal, liquid as well as gas at the room
temperature.
3.28 The increasing order of reactivity among group 1 elements is Li < Na < K < Rb <Cs
whereas that among group 17 elements is F > CI > Br > I. Explain.
3.29 Write the general outer electronic configuration of s-, p-, d- and f- block elements.
3.30 Assign the position of the element having outer electronic configuration
(i) ns2np4 for n=3 (ii) (n-1)d2ns2 for n=4, and (iii) (n-2) f 7 (n-1)d1ns2 for n=6, in the
periodic table.

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 98 chemistry

3.31 The first (∆iH1) and the second (∆iH2) ionization enthalpies (in kJ mol–1) and the (∆egH)
electron gain enthalpy (in kJ mol–1) of a few elements are given below:
Elements ∆H1 ∆H2 ∆egH
I 520 7300 –60
II 419 3051 –48
III 1681 3374 –328
IV 1008 1846 –295
V 2372 5251 +48
VI 738 1451 –40
Which of the above elements is likely to be :
(a) the least reactive element.
(b) the most reactive metal.
(c) the most reactive non-metal.
(d) the least reactive non-metal.
(e) the metal which can form a stable binary halide of the formula MX2(X=halogen).
(f) the metal which can form a predominantly stable covalent halide of the formula
MX (X=halogen)?
3.32 Predict the formulas of the stable binary compounds that would be formed by the
combination of the following pairs of elements.
(a) Lithium and oxygen (b) Magnesium and nitrogen
(c) Aluminium and iodine (d) Silicon and oxygen
(e) Phosphorus and fluorine (f) Element 71 and fluorine
3.33 In the modern periodic table, the period indicates the value of :
(a) atomic number
(b) atomic mass
(c) principal quantum number
(d) azimuthal quantum number.
3.34 Which of the following statements related to the modern periodic table is incorrect?
(a) The p-block has 6 columns, because a maximum of 6 electrons can occupy all
the orbitals in a p-shell.
(b) The d-block has 8 columns, because a maximum of 8 electrons can occupy all
the orbitals in a d-subshell.
(c) Each block contains a number of columns equal to the number of electrons that
can occupy that subshell.
(d) The block indicates value of azimuthal quantum number (l ) for the last subshell
that received electrons in building up the electronic configuration.

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 Classification of Elements and Periodicity in Properties 99

3.35 Anything that influences the valence electrons will affect the chemistry of the
element. Which one of the following factors does not affect the valence shell?
(a) Valence principal quantum number (n)
(b) Nuclear charge (Z )
(c) Nuclear mass
(d) Number of core electrons.
3.36 The size of isoelectronic species — F–, Ne and Na+ is affected by
(a) nuclear charge (Z )
(b) valence principal quantum number (n)
(c) electron-electron interaction in the outer orbitals
(d) none of the factors because their size is the same.
3.37 Which one of the following statements is incorrect in relation to ionization enthalpy?
(a) Ionization enthalpy increases for each successive electron.
(b) The greatest increase in ionization enthalpy is experienced on removal of electron
from core noble gas configuration.
(c) End of valence electrons is marked by a big jump in ionization enthalpy.
(d) Removal of electron from orbitals bearing lower n value is easier than from
orbital having higher n value.
3.38 Considering the elements B, Al, Mg, and K, the correct order of their metallic
character is :
(a) B > Al > Mg > K (b) Al > Mg > B > K
(c) Mg > Al > K > B (d) K > Mg > Al > B
3.39 Considering the elements B, C, N, F, and Si, the correct order of their non-metallic
character is :
(a) B > C > Si > N > F (b) Si > C > B > N > F
(c) F > N > C > B > Si (d) F > N > C > Si > B
3.40 Considering the elements F, Cl, O and N, the correct order of their chemical reactivity
in terms of oxidizing property is :
(a) F > Cl > O > N (b) F > O > Cl > N
(c) Cl > F > O > N (d) O > F > N > Cl

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 Unit 4

CHEMICAL BONDING AND

MOLECULAR STRUCTURE

Scientists are constantly discovering new compounds,

orderly arranging the facts about them, trying to explain
with the existing knowledge, organising to modify the
earlier views or evolve theories for explaining the newly
After studying this Unit, you will be observed facts.
able to
• understand Kössel-Lewis
approach to chemical bonding;

• explain the octet rule and its Matter is made up of one or different type of elements.
limitations, draw Lewis structures Under normal conditions no other element exists as an
of simple molecules; independent atom in nature, except noble gases. However,
• explain the formation of different a group of atoms is found to exist together as one species
types of bonds; having characteristic properties. Such a group of atoms
is called a molecule. Obviously there must be some force
• describe the VSEPR theory and
which holds these constituent atoms together in the
predict the geometry of simple
molecules; molecules. The attractive force which holds various
constituents (atoms, ions, etc.) together in different
• explain the valence bond chemical species is called a chemical bond. Since the
approach for the formation of
formation of chemical compounds takes place as a result of
covalent bonds;
combination of atoms of various elements in different ways,
• predict the directional properties it raises many questions. Why do atoms combine? Why are
of covalent bonds; only certain combinations possible? Why do some atoms
• explain the different types of
combine while certain others do not? Why do molecules
hybridisation involving s, p and possess definite shapes? To answer such questions different
d orbitals and draw shapes of theories and concepts have been put forward from time
simple covalent molecules; to time. These are Kössel-Lewis approach, Valence Shell
Electron Pair Repulsion (VSEPR) Theory, Valence Bond (VB)
• describe the molecular orbital
theory of homonuclear diatomic Theory and Molecular Orbital (MO) Theory. The evolution
molecules; of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to
• explain the concept of hydrogen
the developments in the understanding of the structure
bond.
of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and
bonding is nature’s way of lowering the energy of the system
to attain stability.

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 Chemical Bonding And Molecular Structure 101

4.1 KÖ ssel - L e w i s A p p roach t o the number of valence electrons. This number

Chemical Bonding of valence electrons helps to calculate the
In order to explain the formation of chemical common or group valence of the element.
bond in terms of electrons, a number of The group valence of the elements is generally
attempts were made, but it was only in either equal to the number of dots in Lewis
1916 when Kössel and Lewis succeeded symbols or 8 minus the number of dots or
independently in giving a satisfactory valence electrons.
explanation. They were the first to provide Kössel, in relation to chemical bonding,
some logical explanation of valence which was drew attention to the following facts:
based on the inertness of noble gases. • In the periodic table, the highly
Lewis pictured the atom in terms of a electronegative halogens and the highly
positively charged ‘Kernel’ (the nucleus plus electropositive alkali metals are separated
the inner electrons) and the outer shell that by the noble gases;
could accommodate a maximum of eight • The formation of a negative ion from a
electrons. He, further assumed that these halogen atom and a positive ion from
eight electrons occupy the corners of a cube an alkali metal atom is associated with
which surround the ‘Kernel’. Thus the single the gain and loss of an electron by the
outer shell electron of sodium would occupy respective atoms;
one corner of the cube, while in the case of • The negative and positive ions thus
a noble gas all the eight corners would be formed attain stable noble gas electronic
occupied. This octet of electrons, represents configurations. The noble gases (with the
a particularly stable electronic arrangement. exception of helium which has a duplet
Lewis postulated that atoms achieve of electrons) have a particularly stable
the stable octet when they are linked by outer shell configuration of eight (octet)
chemical bonds. In the case of sodium and electrons, ns2np6.
chlorine, this can happen by the transfer of • The negative and positive ions are stabilized
an electron from sodium to chlorine thereby by electrostatic attraction.
giving the Na+ and Cl– ions. In the case of
other molecules like Cl2, H2, F2, etc., the bond For example, the formation of NaCl from
is formed by the sharing of a pair of electrons sodium and chlorine, according to the above
scheme, can be explained as:
between the atoms. In the process each atom
attains a stable outer octet of electrons. Na → Na+ + e–
Lewis Symbols: In the formation of a [Ne] 3s1 [Ne]
molecule, only the outer shell electrons take Cl + e– → Cl–
part in chemical combination and they are [Ne] 3s2 3p5 [Ne] 3s2 3p6 or [Ar]
known as valence electrons. The inner shell Na+ + Cl– → NaCl or Na+Cl–
electrons are well protected and are generally
not involved in the combination process. Similarly the formation of CaF2 may be
G.N. Lewis, an American chemist introduced shown as:
simple notations to represent valence electrons Ca → Ca2+ + 2e–
in an atom. These notations are called Lewis [Ar]4s2 [Ar]
symbols. For example, the Lewis symbols for F + e– → F–
the elements of second period are as under:
[He] 2s2 2p5 [He] 2s2 2p6 or [Ne]
Ca2+ + 2F– → CaF2 or Ca2+(F– )2
The bond formed, as a result of the
Significance of Lewis Symbols : The electrostatic attraction between the
number of dots around the symbol represents positive and negative ions was termed as

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 102 chemistry

the electrovalent bond. The electrovalence chlorine atoms attain the outer shell octet of
is thus equal to the number of unit charge(s) the nearest noble gas (i.e., argon).
on the ion. Thus, calcium is assigned a
The dots represent electrons. Such
positive electrovalence of two, while chlorine
structures are referred to as Lewis dot
a negative electrovalence of one.
structures.
Kössel’s postulations provide the basis for
The Lewis dot structures can be written for
the modern concepts regarding ion-formation
other molecules also, in which the combining
by electron transfer and the formation of ionic
atoms may be identical or different. The
crystalline compounds. His views have proved
important conditions being that:
to be of great value in the understanding and
• Each bond is formed as a result of sharing
systematisation of the ionic compounds. At
of an electron pair between the atoms.
the same time he did recognise the fact that
a large number of compounds did not fit into • Each combining atom contributes at least
these concepts. one electron to the shared pair.
• The combining atoms attain the outer-
4.1.1 Octet Rule
shell noble gas configurations as a result
Kössel and Lewis in 1916 developed an of the sharing of electrons.
important theory of chemical combination
• Thus in water and carbon tetrachloride
between atoms known as electronic theory
molecules, formation of covalent bonds
of chemical bonding. According to this,
can be represented as:
atoms can combine either by transfer of
valence electrons from one atom to another
(gaining or losing) or by sharing of valence
electrons in order to have an octet in their
valence shells. This is known as octet rule.

4.1.2 Covalent Bond

Langmuir (1919) refined the Lewis
postulations by abandoning the idea of
the stationary cubical arrangement of the
octet, and by introducing the term covalent
bond. The Lewis-Langmuir theory can be Thus, when two atoms share one
understood by considering the formation of electron pair they are said to be joined by
the chlorine molecule, Cl2. The Cl atom with a single covalent bond. In many compounds
electronic configuration, [Ne]3s2 3p5, is one we have multiple bonds between atoms. The
electron short of the argon configuration. formation of multiple bonds envisages sharing
The formation of the Cl­2 molecule can be of more than one electron pair between two
understood in terms of the sharing of a pair atoms. If two atoms share two pairs of
of electrons between the two chlorine atoms, electrons, the covalent bond between them
each chlorine atom contributing one electron is called a double bond. For example, in the
to the shared pair. In the process both carbon dioxide molecule, we have two double
bonds between the carbon and oxygen atoms.
Similarly in ethene molecule the two carbon
atoms are joined by a double bond.

or Cl – Cl
Covalent bond between two Cl atoms Double bonds in CO2 molecule

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 Chemical Bonding And Molecular Structure 103

number of valence electrons. For example,

for the CO32– ion, the two negative charges
indicate that there are two additional
electrons than those provided by the
neutral atoms. For NH +4 ion, one positive
charge indicates the loss of one electron
from the group of neutral atoms.
C2H4 molecule
• Knowing the chemical symbols of the
When combining atoms share three combining atoms and having knowledge
electron pairs as in the case of two nitrogen of the skeletal structure of the compound
atoms in the N2 molecule and the two (known or guessed intelligently), it is easy
carbon atoms in the ethyne molecule, a to distribute the total number of electrons
triple bond is formed. as bonding shared pairs between the
atoms in proportion to the total bonds.
• In general the least electronegative atom
occupies the central position in the
molecule/ion. For example in the NF3 and
N2 molecule CO32–, nitrogen and carbon are the central
atoms whereas fluorine and oxygen
occupy the terminal positions.
• After accounting for the shared pairs of
electrons for single bonds, the remaining
C2H2 molecule electron pairs are either utilized for
multiple bonding or remain as the lone
4.1.3 Lewis Representation of Simple pairs. The basic requirement being
Molecules (the Lewis Structures) that each bonded atom gets an octet of
electrons.
The Lewis dot structures provide a picture
of bonding in molecules and ions in terms of Lewis representations of a few molecules/
the shared pairs of electrons and the octet ions are given in Table 4.1.
rule. While such a picture may not explain
the bonding and behaviour of a molecule Table 4.1 The Lewis Representation of
completely, it does help in understanding the Some Molecules
formation and properties of a molecule to a
large extent. Writing of Lewis dot structures of
molecules is, therefore, very useful. The Lewis
dot structures can be written by adopting the
following steps:
• The total number of electrons required
for writing the structures are obtained
by adding the valence electrons of the
combining atoms. For example, in the CH4
molecule there are eight valence electrons
available for bonding (4 from carbon and
4 from the four hydrogen atoms).
• For anions, each negative charge would
mean addition of one electron. For cations,
each positive charge would result in * Each H atom attains the configuration of helium
subtraction of one electron from the total (a duplet of electrons)

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 104 chemistry

Problem 4.1 each of the oxygen atoms completing the

octets on oxygen atoms. This, however,
Write the Lewis dot structure of CO
does not complete the octet on nitrogen
molecule.
if the remaining two electrons constitute
Solution lone pair on it.
Step 1. Count the total number of valence
electrons of carbon and oxygen atoms.
The outer (valence) shell configurations
of carbon and oxygen atoms are: 2s2 2p2 Hence we have to resort to multiple
and 2s2 2p4, respectively. The valence bonding between nitrogen and one of
electrons available are 4 + 6 =10. the oxygen atoms (in this case a double
bond). This leads to the following Lewis
Step 2. The skeletal structure of CO is
dot structures.
written as: C O
Step 3. Draw a single bond (one shared
electron pair) between C and O and
complete the octet on O, the remaining
two electrons are the lone pair on C.

This does not complete the octet on

carbon and hence we have to resort to
multiple bonding (in this case a triple 4.1.4 Formal Charge
bond) between C and O atoms. This
satisfies the octet rule condition for both Lewis dot structures, in general, do not
atoms. represent the actual shapes of the molecules.
In case of polyatomic ions, the net charge is
possessed by the ion as a whole and not by
a particular atom. It is, however, feasible to
assign a formal charge on each atom. The
formal charge of an atom in a polyatomic
molecule or ion may be defined as the
Problem 4.2
difference between the number of valence
Write the Lewis structure of the nitrite electrons of that atom in an isolated or free
ion, NO2– . state and the number of electrons assigned
to that atom in the Lewis structure. It is
Solution expressed as :
Step 1. Count the total number of
valence electrons of the nitrogen atom, Formal charge (F.C.)
the oxygen atoms and the additional one on an atom in a Lewis =
negative charge (equal to one electron). structure

N(2s2 2p3), O (2s2 2p4)

5 + (2 × 6) +1 = 18 electrons total number of valence total number of non
electrons in the free — bonding (lone pair)
Step 2. The skeletal structure of NO2– is atom electrons
written as : O N O total number of
Step 3. Draw a single bond (one shared — (1/2) bonding (shared)
electrons
electron pair) between the nitrogen and

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 Chemical Bonding And Molecular Structure 105

The counting is based on the assumption 4.1.5 Limitations of the Octet Rule
that the atom in the molecule owns one The octet rule, though useful, is not universal.
electron of each shared pair and both the It is quite useful for understanding the
electrons of a lone pair. structures of most of the organic compounds
Let us consider the ozone molecule (O3). and it applies mainly to the second period
The Lewis structure of O3 may be drawn as: elements of the periodic table. There are three
types of exceptions to the octet rule.
The incomplete octet of the central atom
In some compounds, the number of electrons
surrounding the central atom is less than
eight. This is especially the case with elements
having less than four valence electrons.
The atoms have been numbered as 1, 2 Examples are LiCl, BeH2 and BCl3.
and 3. The formal charge on:
• The central O atom marked 1
1 Li, Be and B have 1, 2 and 3 valence electrons
=6–2– (6) = +1 only. Some other such compounds are AlCl3
2
and BF3.
• The end O atom marked 2
Odd-electron molecules
1
=6–4– (4) = 0 In molecules with an odd number of electrons
2
like nitric oxide, NO and nitrogen dioxide,
• The end O atom marked 3 NO2, the octet rule is not satisfied for all the
1 atoms
=6–6– (2) = –1
2
Hence, we represent O3 along with the
formal charges as follows: The expanded octet
Elements in and beyond the third period of
the periodic table have, apart from 3s and 3p
orbitals, 3d orbitals also available for bonding.
In a number of compounds of these elements
there are more than eight valence electrons
We must understand that formal charges around the central atom. This is termed as
do not indicate real charge separation within the expanded octet. Obviously the octet rule
the molecule. Indicating the charges on the does not apply in such cases.
atoms in the Lewis structure only helps in
Some of the examples of such compounds
keeping track of the valence electrons in
are: PF 5 , SF 6 , H 2 SO 4 and a number of
the molecule. Formal charges help in the
coordination compounds.
selection of the lowest energy structure from
a number of possible Lewis structures for a
given species. Generally the lowest energy
structure is the one with the smallest
formal charges on the atoms. The formal
charge is a factor based on a pure covalent
view of bonding in which electron pairs
are shared equally by neighbouring atoms.

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 106 chemistry

Interestingly, sulphur also forms many affinity, is the negative of the energy change
compounds in which the octet rule is obeyed. accompanying electron gain.
In sulphur dichloride, the S atom has an octet Obviously ionic bonds will be formed
of electrons around it. more easily between elements with
comparatively low ionization enthalpies
and elements with comparatively high
negative value of electron gain enthalpy.
Other drawbacks of the octet theory
Most ionic compounds have cations
• It is clear that octet rule is based upon derived from metallic elements and anions
the chemical inertness of noble gases. from non-metallic elements. The ammonium
However, some noble gases (for example ion, NH 4+ (made up of two non-metallic
xenon and krypton) also combine with elements) is an exception. It forms the cation
oxygen and fluorine to form a number of of a number of ionic compounds.
compounds like XeF2, KrF2, XeOF2 etc.
Ionic compounds in the crystalline
• This theory does not account for the shape state consist of orderly three-dimensional
of molecules. arrangements of cations and anions held
• It does not explain the relative stability of together by coulombic interaction energies.
the molecules being totally silent about These compounds crystallise in different
the energy of a molecule. crystal structures determined by the size of
the ions, their packing arrangements and
4.2 Ionic or Electrovalent Bond other factors. The crystal structure of sodium
From the Kössel and Lewis treatment of the chloride, NaCl (rock salt), for example is
formation of an ionic bond, it follows that the shown below.
formation of ionic compounds would primarily
depend upon:
• The ease of formation of the positive and
negative ions from the respective neutral
atoms;
• The arrangement of the positive and
negative ions in the solid, that is, the
lattice of the crystalline compound.
The formation of a positive ion involves
ionization, i.e., removal of electron(s) from
the neutral atom and that of the negative
ion involves the addition of electron(s) to the Rock salt structure
neutral atom.
In ionic solids, the sum of the electron gain
M(g) → M+(g) + e– ;
enthalpy and the ionization enthalpy may be
Ionization enthalpy positive but still the crystal structure gets
X(g) + e– → X – (g) ; stabilized due to the energy released in the
Electron gain enthalpy formation of the crystal lattice. For example:
the ionization enthalpy for Na+(g) formation
M+(g) + X –(g) → MX(s)
from Na(g) is 495.8 kJ mol–1 ; while the electron
The electron gain enthalpy, ∆eg H, is the gain enthalpy for the change Cl(g) + e–→
enthalpy change (Unit 3), when a gas phase Cl– (g) is, – 348.7 kJ mol–1 only. The sum of the
atom in its ground state gains an electron. two, 147.1 kJ mol-1 is more than compensated
The electron gain process may be exothermic for by the enthalpy of lattice formation of
or endothermic. The ionization, on the other NaCl(s) (–788 kJ mol–1). Therefore, the energy
hand, is always endothermic. Electron released in the processes is more than the

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Unit [Link] 106 9/12/2022 [Link] AM

 Chemical Bonding And Molecular Structure 107

energy absorbed. Thus a qualitative measure

of the stability of an ionic compound
is provided by its enthalpy of lattice
formation and not simply by achieving
octet of electrons around the ionic species
in gaseous state.
Since lattice enthalpy plays a key role
in the formation of ionic compounds, it is
important that we learn more about it.
4.2.1 Lattice Enthalpy
The Lattice Enthalpy of an ionic solid
is defined as the energy required to
completely separate one mole of a solid
ionic compound into gaseous constituent
ions. For example, the lattice enthalpy of
NaCl is 788 kJ mol–1. This means that 788 Fig. 4.1 The bond length in a covalent
kJ of energy is required to separate one mole molecule AB.
of solid NaCl into one mole of Na+ (g) and one R = rA + rB (R is the bond length and rA and rB are
mole of Cl– (g) to an infinite distance. the covalent radii of atoms A and B
respectively)
This process involves both the attractive
forces between ions of opposite charges
in the same molecule. The van der Waals
and the repulsive forces between ions of radius represents the overall size of the
like charge. The solid crystal being three- atom which includes its valence shell in a
dimensional; it is not possible to calculate nonbonded situation. Further, the van der
lattice enthalpy directly from the interaction Waals radius is half of the distance between
of forces of attraction and repulsion only. two similar atoms in separate molecules in
Factors associated with the crystal geometry a solid. Covalent and van der Waals radii of
have to be included. chlorine are depicted in Fig. 4.2.
4.3 Bond Parameters
rc = 99 pm 19
4.3.1 Bond Length 8
pm
Bond length is defined as the equilibrium
distance between the nuclei of two bonded
atoms in a molecule. Bond lengths are
measured by spectroscopic, X-ray diffraction
and electron-diffraction techniques about
which you will learn in higher classes. Each
atom of the bonded pair contributes to the
r vd
w
=

bond length (Fig. 4.1). In the case of a covalent

18
0

bond, the contribution from each atom is

pm

called the covalent radius of that atom.

pm
0
36

The covalent radius is measured

approximately as the radius of an atom’s
Fig. 4.2 Covalent and van der Waals radii in
core which is in contact with the core of an a chlorine molecule. The inner circles
adjacent atom in a bonded situation. The correspond to the size of the chlorine
covalent radius is half of the distance between atom (rvdw and rc are van der Waals and
two similar atoms joined by a covalent bond covalent radii respectively).

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 108 chemistry

Some typical average bond lengths for Table 4.2 Average Bond Lengths for Some
single, double and triple bonds are shown in Single, Double and Triple Bonds
Table 4.2. Bond lengths for some common
Covalent Bond
molecules are given in Table 4.3. Bond Type
Length (pm)
The covalent radii of some common
O–H 96
elements are listed in Table 4.4.
C–H 107
4.3.2 Bond Angle N–O 136
C–O 143
It is defined as the angle between the orbitals
C–N 143
containing bonding electron pairs around the C–C 154
central atom in a molecule/complex ion. Bond C=O 121
angle is expressed in degree which can be N=O 122
experimentally determined by spectroscopic C=C 133
methods. It gives some idea regarding the C=N 138
distribution of orbitals around the central C≡N 116
atom in a molecule/complex ion and hence it C≡C 120
helps us in determining its shape. For
Table 4.3 Bond Lengths in Some Common
example H–O–H bond angle in water can be
Molecules
represented as under :
Molecule Bond Length (pm)
H2 (H – H) 74
F2 (F – F) 144
4.3.3 Bond Enthalpy Cl2 (Cl – Cl) 199
It is defined as the amount of energy required Br2 (Br – Br) 228
to break one mole of bonds of a particular I2 (I – I) 267
type between two atoms in a gaseous state. N2 (N ≡ N) 109
The unit of bond enthalpy is kJ mol–1. For O2 (O = O) 121
example, the H – H bond enthalpy in hydrogen HF (H – F) 92
molecule is 435.8 kJ mol–1. HCl (H – Cl) 127
HBr (H – Br) 141
H2(g) → H(g) + H(g); ∆aH = 435.8 kJ mol–1
HI (H – I) 160
Similarly the bond enthalpy for molecules
containing multiple bonds, for example O2 and Table 4.4 Covalent Radii, *rcov/(pm)
N2 will be as under :
O2 (O = O) (g) → O(g) + O(g);
∆aH = 498 kJ mol–1
N2 (N ≡ N) (g) → N(g) + N(g);
∆aH = 946.0 kJ mol–1
It is important that larger the bond
dissociation enthalpy, stronger will be the
bond in the molecule. For a heteronuclear
diatomic molecules like HCl, we have
HCl (g) → H(g) + Cl (g); ∆aH = 431.0 kJ mol–1
In case of polyatomic molecules, the
measurement of bond strength is more
complicated. For example in case  o f H 2O * The values cited are for single bonds, except where
molecule, the enthalpy needed to break the otherwise indicated in parenthesis. (See also Unit 3 for
two O – H bonds is not the same. periodic trends).

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 Chemical Bonding And Molecular Structure 109

H2O(g) → H(g) + OH(g); ∆aH1 = 502 kJ mol–1

OH(g) → H(g) + O(g); ∆aH2 = 427 kJ mol–1
The difference in the ∆aH value shows
that the second O – H bond undergoes
some change because of changed chemical
environment. This is the reason for some
difference in energy of the same O – H bond
in different molecules like C2H5OH (ethanol)
and water. Therefore in polyatomic molecules
the term mean or average bond enthalpy
is used. It is obtained by dividing total bond
dissociation enthalpy by the number of bonds
broken as explained below in case of water
molecule,
502 + 427 Fig. 4.3 Resonance in the O3 molecule
Average bond enthalpy =
2
(structures I and II represent the two canonical
= 464.5 kJ mol–1 forms while the structure III is the resonance hybrid)
4.3.4 Bond Order
In the Lewis description of covalent bond, In both structures we have a O–O single
the Bond Order is given by the number bond and a O=O double bond. The normal
of bonds between the two atoms in a O–O and O=O bond lengths are 148 pm
molecule. The bond order, for example in and 121 pm respectively. Experimentally
H2 (with a single shared electron pair), in O2 determined oxygen-oxygen bond lengths in
(with two shared electron pairs) and in N2 the O3 molecule are same (128 pm). Thus the
(with three shared electron pairs) is 1,2,3 oxygen-oxygen bonds in the O3 molecule are
respectively. Similarly in CO (three shared intermediate between a double and a single
electron pairs between C and O) the bond bond. Obviously, this cannot be represented
order is 3. For N2, bond order is 3 and its by either of the two Lewis structures shown
is 946 kJ mol–1; being one of the highest above.
for a diatomic molecule. The concept of resonance was introduced
Isoelectronic molecules and ions have to deal with the type of difficulty experienced
identical bond orders; for example, F2 and in the depiction of accurate structures of
O22– have bond order 1. N2, CO and NO+ have molecules like O3. According to the concept
bond order 3. of resonance, whenever a single Lewis
A general correlation useful for structure cannot describe a molecule
understanding the stablities of molecules accurately, a number of structures with
is that: with increase in bond order, similar energy, positions of nuclei, bonding
bond enthalpy increases and bond length and non-bonding pairs of electrons are
decreases. taken as the canonical structures of the
hybrid which describes the molecule
4.3.5 Resonance Structures accurately. Thus for O3, the two structures
It is often observed that a single Lewis structure shown above constitute the canonical
is inadequate for the representation of a structures or resonance structures and
molecule in conformity with its experimentally their hybrid i.e., the III structure represents
determined parameters. For example, the the structure of O3 more accurately. This is
ozone, O3 molecule can be equally represented also called resonance hybrid. Resonance is
by the structures I and II shown below: represented by a double headed arrow.

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 110 chemistry

Some of the other examples of resonance

structures are provided by the carbonate ion
and the carbon dioxide molecule.

Problem 4.3 Fig. 4.5 Resonance in CO 2 molecule, I, II

and III represent the three canonical
Explain the structure of CO32– ion in forms.
terms of resonance.
Solution In general, it may be stated that
The single Lewis structure based on • Resonance stabilizes the molecule as the
the presence of two single bonds and energy of the resonance hybrid is less
one double bond between carbon than the energy of any single cannonical
and oxygen atoms is inadequate to structure; and,
represent the molecule accurately as it
represents unequal bonds. According
• Resonance averages the bond
characteristics as a whole.
to the experimental findings, all carbon
to oxygen bonds in CO32– are equivalent. Thus the energy of the O 3 resonance
Therefore the carbonate ion is best hybrid is lower than either of the two
described as a resonance hybrid of the cannonical froms I and II (Fig. 4.3).
canonical forms I, II, and III shown below.
Many misconceptions are associated
with resonance and the same need to be
dispelled. You should remember that :
• The cannonical forms have no real
existence.
• The molecule does not exist for a certain
fraction of time in one cannonical form
and for other fractions of time in other
Fig. 4.4 Resonance in CO32–, I, II and III cannonical forms.
represent the three canonical • There is no such equilibrium between
forms. the cannonical forms as we have
Problem 4.4 between tautomeric forms (keto and
Explain the structure of CO2 molecule. enol) in tautomerism.
• The molecule as such has a single
Solution structure which is the resonance
The experimentally determined carbon hybrid of the cannonical forms and
to oxygen bond length in CO 2 is which cannot as such be depicted by
115 pm. The lengths of a normal a single Lewis structure.
carbon to oxygen double bond (C=O)
and carbon to oxygen triple bond (C≡O) 4.3.6 Polarity of Bonds
are 121 pm and 110 pm respectively.
The carbon-oxygen bond lengths in The existence of a hundred percent ionic or
CO2 (115 pm) lie between the values covalent bond represents an ideal situation.
for C=O and C≡O. Obviously, a single In reality no bond or a compound is either
Lewis structure cannot depict this completely covalent or ionic. Even in case of
position and it becomes necessary to covalent bond between two hydrogen atoms,
write more than one Lewis structures there is some ionic character.
and to consider that the structure of
CO2 is best described as a hybrid of When covalent bond is formed between
the canonical or resonance forms I, II two similar atoms, for example in H2, O2,
and III. Cl2, N2 or F2, the shared pair of electrons is
equally attracted by the two atoms. As a result

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 Chemical Bonding And Molecular Structure 111

electron pair is situated exactly between the In case of polyatomic molecules the dipole
two identical nuclei. The bond so formed is moment not only depend upon the individual
called nonpolar covalent bond. Contrary to dipole moments of bonds known as bond
this in case of a heteronuclear molecule like dipoles but also on the spatial arrangement
HF, the shared electron pair between the two of various bonds in the molecule. In such
atoms gets displaced more towards fluorine case, the dipole moment of a molecule is the
since the electronegativity of fluorine (Unit 3) vector sum of the dipole moments of various
is far greater than that of hydrogen. The bonds. For example in H2O molecule, which
resultant covalent bond is a polar covalent has a bent structure, the two O–H bonds are
bond. oriented at an angle of 104.50. Net dipole
As a result of polarisation, the molecule moment of 6.17 × 10–30 C m (1D = 3.33564
possesses the dipole moment (depicted × 10–30 C m) is the resultant of the dipole
below) which can be defined as the product of moments of two O–H bonds.
the magnitude of the charge and the distance
between the centres of positive and negative
charge. It is usually designated by a Greek
letter ‘µ’. Mathematically, it is expressed as
follows :
Dipole moment (µ) = charge (Q) × distance of
separation (r)
Dipole moment is usually expressed in Net Dipole moment, µ = 1.85 D
Debye units (D). The conversion factor is = 1.85 × 3.33564 × 10–30 C m = 6.17 ×10–30 C m
1 D = 3.33564 × 10–30 C m
The dipole moment in case of BeF2 is zero.
where C is coulomb and m is meter.
This is because the two equal bond dipoles
Further dipole moment is a vector quantity point in opposite directions and cancel the
and by convention it is depicted by a small effect of each other.
arrow with tail on the negative centre and
head pointing towards the positive centre.
But in chemistry presence of dipole moment
is represented by the crossed arrow ( )
put on Lewis structure of the molecule. The In tetra-atomic molecule, for example in
cross is on positive end and arrow head is on BF3, the dipole moment is zero although the
negative end. For example the dipole moment B – F bonds are oriented at an angle of 120o
of HF may be represented as : to one another, the three bond moments give
a net sum of zero as the resultant of any two
H F
is equal and opposite to the third.
This arrow symbolises the direction of the
shift of electron density in the molecule. Note
that the direction of crossed arrow is opposite
to the conventional direction of dipole moment
vector.

Peter Debye, the Dutch chemist

received Nobel prize in 1936 for
Let us study an interesting case of NH3
his work on X-ray diffraction and
dipole moments. The magnitude
and NF3 molecule. Both the molecules have
of the dipole moment is given in pyramidal shape with a lone pair of electrons
Debye units in order to honour him. on nitrogen atom. Although fluorine is more
electronegative than nitrogen, the resultant

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 112 chemistry

dipole moment of NH3 (4.90 × 10–30 C m) is • The smaller the size of the cation and the
greater than that of NF3 (0.8 × 10–30 C m). This larger the size of the anion, the greater
is because, in case of NH3 the orbital dipole the covalent character of an ionic bond.
due to lone pair is in the same direction as • The greater the charge on the cation, the
the resultant dipole moment of the N – H greater the covalent character of the ionic
bonds, whereas in NF3 the orbital dipole is in bond.
the direction opposite to the resultant dipole
• For cations of the same size and charge,
moment of the three N–F bonds. The orbital
the one, with electronic configuration
dipole because of lone pair decreases the effect
(n-1)dnnso, typical of transition metals, is
of the resultant N – F bond moments, which
more polarising than the one with a noble
results in the low dipole moment of NF3 as
gas configuration, ns2 np6, typical of alkali
represented below :
and alkaline earth metal cations.
The cation polarises the anion, pulling
the electronic charge toward itself and
thereby increasing the electronic charge
between the two. This is precisely what
happens in a covalent bond, i.e., buildup
of electron charge density between the
nuclei. The polarising power of the cation,
the polarisability of the anion and the
extent of distortion (polarisation) of anion
are the factors, which determine the per
Dipole moments of some molecules are cent covalent character of the ionic bond.
shown in Table 4.5.
Just as all the covalent bonds have 4.4 The Valence Shell Electron
some partial ionic character, the ionic Pair Repulsion (VSEPR) Theory
bonds also have partial covalent character. As already explained, Lewis concept is unable
The partial covalent character of ionic to explain the shapes of molecules. This
bonds was discussed by Fajans in terms of theory provides a simple procedure to predict
the following rules: the shapes of covalent molecules. Sidgwick
Table 4.5 Dipole Moments of Selected Molecules

Dipole
Type of Molecule Example Geometry
Moment, µ(D)
Molecule (AB) HF 1.78 linear
HCl 1.07 linear
HBr 0.79 linear
Hl 0.38 linear
H2 0 linear
Molecule (AB2) H2O 1.85 bent
H2S 0.95 bent
CO2 0 linear
Molecule (AB3) NH3 1.47 trigonal-pyramidal
NF3 0.23 trigonal-pyramidal
BF3 0 trigonal-planar
Molecule (AB4) CH4 0 tetrahedral
CHCl3 1.04 tetrahedral
CCl4 0 tetrahedral

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 Chemical Bonding And Molecular Structure 113

and Powell in 1940, proposed a simple theory result in deviations from idealised shapes and
based on the repulsive interactions of the alterations in bond angles in molecules.
electron pairs in the valence shell of the For the prediction of geometrical shapes
atoms. It was further developed and redefined of molecules with the help of VSEPR theory,
by Nyholm and Gillespie (1957). it is convenient to divide molecules into
The main postulates of VSEPR theory are two categories as (i) molecules in which
as follows: the central atom has no lone pair and
• The shape of a molecule depends upon (ii) molecules in which the central atom
the number of valence shell electron pairs has one or more lone pairs.
(bonded or nonbonded) around the central Table 4.6 (page114) shows the
atom. arrangement of electron pairs about a
• Pairs of electrons in the valence shell repel central atom A (without any lone pairs) and
one another since their electron clouds are geometries of some molecules/ions of the type
negatively charged. AB. Table 4.7 (page 115) shows shapes of some
simple molecules and ions in which the central
• These pairs of electrons tend to occupy
atom has one or more lone pairs. Table 4.8
such positions in space that minimise
(page 116) explains the reasons for the
repulsion and thus maximise distance
distortions in the geometry of the molecule.
between them.
• The valence shell is taken as a sphere As depicted in Table 4.6, in the
with the electron pairs localising on the compounds of AB2, AB3, AB4, AB5 and AB6,
spherical surface at maximum distance the arrangement of electron pairs and the
from one another. B atoms around the central atom A are :
linear, trigonal planar, tetrahedral,
• A multiple bond is treated as if it is a single trigonal-bipyramidal and octahedral,
electron pair and the two or three electron respectively. Such arrangement can be seen
pairs of a multiple bond are treated as a
in the molecules like BF3 (AB3), CH4 (AB4) and
single super pair.
PCl5 (AB5) as depicted below by their ball and
• Where two or more resonance structures stick models.
can represent a molecule, the VSEPR
model is applicable to any such structure.
The repulsive interaction of electron pairs
decrease in the order:
Lone pair (lp) – Lone pair (lp) > Lone pair
(lp) – Bond pair (bp) > Bond pair (bp) –
Bond pair (bp) Fig. 4.6 The shapes of molecules in which
central atom has no lone pair
Nyholm and Gillespie (1957) refined the
VSEPR model by explaining the important The VSEPR Theory is able to predict
difference between the lone pairs and bonding geometry of a large number of molecules,
pairs of electrons. While the lone pairs are especially the compounds of p-block elements
localised on the central atom, each bonded accurately. It is also quite successful in
pair is shared between two atoms. As a result, determining the geometry quite-accurately
the lone pair electrons in a molecule occupy even when the energy difference between
more space as compared to the bonding pairs possible structures is very small. The
of electrons. This results in greater repulsion theoretical basis of the VSEPR theory regarding
between lone pairs of electrons as compared the effects of electron pair repulsions on
to the lone pair - bond pair and bond pair - molecular shapes is not clear and continues
bond pair repulsions. These repulsion effects to be a subject of doubt and discussion.

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 114 chemistry

Table 4.6 Geometry of Molecules in which the Central Atom has No Lone Pair of Electrons

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 Chemical Bonding And Molecular Structure 115

Table 4.7 Shape (geometry) of Some Simple Molecules/Ions with Central Ions having
One or More Lone Pairs of Electrons(E).

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 116 chemistry

Table 4.8 Shapes of Molecules containing Bond Pair and Lone Pair
Molecule No. of No. of Arrangement Shape Reason for the
type bonding lone of electrons shape acquired
pairs pairs

AB2E 4 1 Bent Theoretically the shape

should have been triangular
planar but actually it is found
to be bent or v-shaped. The
reason being the lone pair-
bond pair repulsion is much
more as compared to the bond
pair-bond pair repulsion. So
the angle is reduced to 119.5°
from 120°.

AB3E 3 1 Trigonal Had there been a bp in place

of lp the shape would have
pyramidal
been tetrahedral but one
lone pair is present and due
to the repulsion between
lp-bp (which is more than
bp-bp repulsion) the angle
between bond pairs is
reduced to 107° from 109.5°.

Bent The shape should have been

AB2E2 2 2 tetrahedral if there were all bp
but two lp are present so the
shape is distorted tetrahedral
or angular. The reason is
lp-lp repulsion is more than
lp-bp repulsion which is more
than bp-bp repulsion. Thus,
the angle is reduced to 104.5°
from 109.5°.

AB4E 4 1 See- In (a) the lp is present at axial

saw position so there are three
lp—bp repulsions at 90°.
In(b) the lp is in an equatorial
position, and there are two
lp—bp repulsions. Hence,
arrangement (b) is more
stable. The shape shown in
(b) is described as a distorted
tetrahedron, a folded square
(More stable) or a see-saw.

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 Chemical Bonding And Molecular Structure 117

Molecule No. of No. of Arrangement Shape Reason for the

type bonding lone of electrons shape acquired
pairs pairs

AB3E2 3 2 T-shape In (a) the lp are at

equatorial position
so there are less lp-
bp repulsions as
compared to others
in which the lp are
at axial positions. So
structure (a) is most
stable. (T-shaped).

4.5 Valence Bond Theory of the valence bond theory is based on the
As we know that Lewis approach helps in knowledge of atomic orbitals, electronic
writing the structure of molecules but it configurations of elements (Units 2), the
fails to explain the formation of chemical overlap criteria of atomic orbitals, the
bond. It also does not give any reason for the hybridization of atomic orbitals and the
principles of variation and superposition. A
difference in bond dissociation enthalpies and
rigorous treatment of the VB theory in terms
bond lengths in molecules like H2 (435.8 kJ
of these aspects is beyond the scope of this
mol-1, 74 pm) and F2 (155 kJ mol-1, 144 pm),
book. Therefore, for the sake of convenience,
although in both the cases a single covalent
valence bond theory has been discussed in
bond is formed by the sharing of an electron
terms of qualitative and non-mathematical
pair between the respective atoms. It also treatment only. To start with, let us consider
gives no idea about the shapes of polyatomic the formation of hydrogen molecule which is
molecules. the simplest of all molecules.
Similarly the VSEPR theory gives the Consider two hydrogen atoms A and B
geometry of simple molecules but theoretically, approaching each other having nuclei NA
it does not explain them and also it has limited and NB and electrons present in them are
applications. To overcome these limitations represented by eA and eB. When the two atoms
the two important theories based on quantum are at large distance from each other, there
mechanical principles are introduced. These is no interaction between them. As these two
are valence bond (VB) theory and molecular atoms approach each other, new attractive
orbital (MO) theory. and repulsive forces begin to operate.
Valence bond theory was introduced Attractive forces arise between:
by Heitler and London (1927) and developed (i) nucleus of one atom and its own electron
further by Pauling and others. A discussion that is NA – eA and NB– eB.

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 118 chemistry

(ii) nucleus of one atom and electron of together to form a stable molecule having the
other atom i.e., NA– eB, NB– eA. bond length of 74 pm.
Similarly repulsive forces arise between Since the energy gets released when the
(i) electrons of two atoms like eA – eB, bond is formed between two hydrogen atoms,
the hydrogen molecule is more stable than
(ii) nuclei of two atoms NA – NB.
that of isolated hydrogen atoms. The energy
Attractive forces tend to bring the two so released is called as bond enthalpy, which
atoms close to each other whereas repulsive is corresponding to minimum in the curve
forces tend to push them apart (Fig. 4.7). depicted in Fig. 4.8. Conversely, 435.8 kJ of
energy is required to dissociate one mole of
H2 molecule.
H2(g) + 435.8 kJ mol–1 → H(g) + H(g)

Fig. 4.8 The potential energy curve for the

formation of H2 molecule as a function
of internuclear distance of the H atoms.
The minimum in the curve corresponds
to the most stable state of H2.

4.5.1 Orbital Overlap Concept

In the formation of hydrogen molecule,
there is a minimum energy state when two
hydrogen atoms are so near that their atomic
Fig. 4.7 Forces of attraction and repulsion
orbitals undergo partial interpenetration. This
during the formation of H2 molecule partial merging of atomic orbitals is called
overlapping of atomic orbitals which results in
Experimentally it has been found that
the pairing of electrons. The extent of overlap
the magnitude of new attractive force is
decides the strength of a covalent bond. In
more than the new repulsive forces. As a
result, two atoms approach each other and general, greater the overlap the stronger is the
potential energy decreases. Ultimately a stage bond formed between two atoms. Therefore,
is reached where the net force of attraction according to orbital overlap concept, the
balances the force of repulsion and system formation of a covalent bond between two
acquires minimum energy. At this stage atoms results by pairing of electrons present
two hydrogen atoms are said to be bonded in the valence shell having opposite spins.

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 Chemical Bonding And Molecular Structure 119

4.5.2 Directional Properties of Bonds

As we have already seen, the covalent bond
is formed by overlapping of atomic orbitals.
The molecule of hydrogen is formed due to the
overlap of 1s-orbitals of two H atoms.
In case of polyatomic molecules like CH4,
NH3 and H2O, the geometry of the molecules
is also important in addition to the bond
formation. For example why is it so that CH4
molecule has tetrahedral shape and HCH
bond angles are 109.5°? Why is the shape of
NH3 molecule pyramidal ?
The valence bond theory explains the
shape, the formation and directional properties
of bonds in polyatomic molecules like CH4,
NH3 and H2O, etc. in terms of overlap and
hybridisation of atomic orbitals.
4.5.3 Overlapping of Atomic Orbitals
When orbitals of two atoms come close to form
bond, their overlap may be positive, negative
or zero depending upon the sign (phase) and
direction of orientation of amplitude of orbital
wave function in space (Fig. 4.9). Positive and
negative sign on boundary surface diagrams
in the Fig. 4.9 show the sign (phase) of orbital
wave function and are not related to charge.
Orbitals forming bond should have same sign Fig.4.9 Positive, negative and zero overlaps of
s and p atomic orbitals
(phase) and orientation in space. This is called
positive overlap. Various overlaps of s and p hydrogen. The four atomic orbitals of carbon,
orbitals are depicted in Fig. 4.9. each with an unpaired electron can overlap
with the 1s orbitals of the four H atoms which
The criterion of overlap, as the main factor are also singly occupied. This will result in the
for the formation of covalent bonds applies formation of four C-H bonds. It will, however,
uniformly to the homonuclear/heteronuclear be observed that while the three p orbitals of
diatomic molecules and polyatomic molecules. carbon are at 90° to one another, the HCH
We know that the shapes of CH4, NH3, and angle for these will also be 90°. That is three
H2O molecules are tetrahedral, pyramidal C-H bonds will be oriented at 90° to one
and bent respectively. It would be therefore another. The 2s orbital of carbon and the 1s
interesting to use VB theory to find out if these orbital of H are spherically symmetrical and
geometrical shapes can be explained in terms they can overlap in any direction. Therefore
of the orbital overlaps. the direction of the fourth C-H bond cannot
Let us first consider the CH4 (methane) be ascertained. This description does not fit
molecule. The electronic configuration of in with the tetrahedral HCH angles of 109.5°.
carbon in its ground state is [He]2s2 2p2 which Clearly, it follows that simple atomic orbital
in the excited state becomes [He] 2s1 2px1 2py1 overlap does not account for the directional
2pz1. The energy required for this excitation is characteristics of bonds in CH4. Using similar
compensated by the release of energy due to procedure and arguments, it can be seen that in
overlap between the orbitals of carbon and the the case of NH3 and H2O molecules, the HNH

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 120 chemistry

and HOH angles should be 90°. This is in above and below the plane of the
disagreement with the actual bond angles of participating atoms.
107° and 104.5° in the NH3 and H2O molecules
respectively.
4.5.4 Types of Overlapping and Nature of
Covalent Bonds
The covalent bond may be classified into
two types depending upon the types of
overlapping:
(i) Sigma(σ) bond, and (ii) pi(π) bond
(i) Sigma(σ) bond : This type of covalent 4.5.5 Strength of Sigma and pi Bonds
bond is formed by the end to end (head- Basically the strength of a bond depends
on) overlap of bonding orbitals along the upon the extent of overlapping. In case of
internuclear axis. This is called as head sigma bond, the overlapping of orbitals takes
on overlap or axial overlap. This can be place to a larger extent. Hence, it is stronger
formed by any one of the following types
as compared to the pi bond where the extent
of combinations of atomic orbitals.
of overlapping occurs to a smaller extent.
• s-s overlapping : In this case, there is Further, it is important to note that in the
overlap of two half filled s-orbitals along formation of multiple bonds between two
the internuclear axis as shown below : atoms of a molecule, pi bond(s) is formed in
addition to a sigma bond.

4.6 Hybridisation
In order to explain the characteristic
geometrical shapes of polyatomic molecules
• s-p overlapping: This type of overlap like CH4, NH3 and H2O etc., Pauling introduced
occurs between half filled s-orbitals of one the concept of hybridisation. According to him
atom and half filled p-orbitals of another the atomic orbitals combine to form new set of
atom. equivalent orbitals known as hybrid orbitals.
Unlike pure orbitals, the hybrid orbitals are
used in bond formation. The phenomenon is
known as hybridisation which can be defined
as the process of intermixing of the orbitals of
• p–p overlapping : This type of overlap slightly different energies so as to redistribute
takes place between half filled p-orbitals their energies, resulting in the formation of
of the two approaching atoms. new set of orbitals of equivalent energies and
shape. For example when one 2s and three
2p-orbitals of carbon hybridise, there is the
formation of four new sp3 hybrid orbitals.
Salient features of hybridisation: The main
(ii) pi( ) bond : In the formation of π bond features of hybridisation are as under :
the atomic orbitals overlap in such a
way that their axes remain parallel to 1. The number of hybrid orbitals is equal to
each other and perpendicular to the the number of the atomic orbitals that get
internuclear axis. The orbitals formed hybridised.
due to sidewise overlapping consists 2. The hybridised orbitals are always
of two saucer type charged clouds equivalent in energy and shape.

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3. The hybrid orbitals are more effective in vacant 2p orbital to account for its bivalency.
forming stable bonds than the pure atomic One 2s and one 2p-orbital gets hybridised to
orbitals. form two sp hybridised orbitals. These two
4. These hybrid orbitals are directed in sp hybrid orbitals are oriented in opposite
space in some preferred direction to have direction forming an angle of 180°. Each of
minimum repulsion between electron the sp hybridised orbital overlaps with the
pairs and thus a stable arrangement. 2p-orbital of chlorine axially and form two Be-
Therefore, the type of hybridisation Cl sigma bonds. This is shown in Fig. 4.10.
indicates the geometry of the molecules.
Important conditions for hybridisation
(i) The orbitals present in the valence shell
of the atom are hybridised.
Be
(ii) The orbitals undergoing hybridisation
should have almost equal energy.
(iii) Promotion of electron is not essential
condition prior to hybridisation.
(iv) It is not necessary that only half filled
orbitals participate in hybridisation.
In some cases, even filled orbitals of
valence shell take part in hybridisation.
Fig.4.10 (a) Formation of sp hybrids from s and
4.6.1 Types of Hybridisation p orbitals; (b) Formation of the linear
There are various types of hybridisation BeCl2 molecule
involving s, p and d orbitals. The different
(II) sp2 hybridisation : In this hybridisation
types of hybridisation are as under:
there is involvement of one s and two
(I) sp hybridisation: This type of hybridisation p-orbitals in order to form three equivalent
involves the mixing of one s and one p orbital sp 2 hybridised orbitals. For example, in
resulting in the formation of two equivalent BCl3 molecule, the ground state electronic
sp hybrid orbitals. The suitable orbitals for configuration of central boron atom is
sp hybridisation are s and pz, if the hybrid 1s22s22p1. In the excited state, one of the 2s
orbitals are to lie along the z-axis. Each sp electrons is promoted to vacant 2p orbital as
hybrid orbitals has 50% s-character and
50% p-character. Such a molecule in which
the central atom is sp-hybridised and linked
directly to two other central atoms possesses
linear geometry. This type of hybridisation is
also known as diagonal hybridisation.
The two sp hybrids point in the opposite
direction along the z-axis with projecting
positive lobes and very small negative lobes,
which provides more effective overlapping
resulting in the formation of stronger bonds.
Example of molecule having sp
hybridisation
B e C l 2: T h e g r o u n d s t a t e e l e c t r o n i c
configuration of Be is 1s22s2. In the exited Fig.4.11 Formation of sp2 hybrids and the BCl3
state one of the 2s-electrons is promoted to molecule

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a result boron has three unpaired electrons. 2 1 1 1

ground state is 2S 2 p x 2 py 2 p z having three
These three orbitals (one 2s and two 2p)
unpaired electrons in the sp3 hybrid orbitals
hybridise to form three sp2 hybrid orbitals.
and a lone pair of electrons is present in the
The three hybrid orbitals so formed are
fourth one. These three hybrid orbitals overlap
oriented in a trigonal planar arrangement
with 1s orbitals of hydrogen atoms to form
and overlap with 2p orbitals of chlorine to
three N–H sigma bonds. We know that the
form three B-Cl bonds. Therefore, in BCl3
force of repulsion between a lone pair and a
(Fig. 4.11), the geometry is trigonal planar
bond pair is more than the force of repulsion
with ClBCl bond angle of 120°.
between two bond pairs of electrons. The
(III) sp 3 hybridisation: This type of molecule thus gets distorted and the bond
hybridisation can be explained by taking the angle is reduced to 107° from 109.5°. The
example of CH4 molecule in which there is geometry of such a molecule will be pyramidal
mixing of one s-orbital and three p-orbitals as shown in Fig. 4.13.
of the valence shell to form four sp3 hybrid
orbital of equivalent energies and shape. There
is 25% s-character and 75% p-character in
each sp3 hybrid orbital. The four sp3 hybrid
orbitals so formed are directed towards the
four corners of the tetrahedron. The angle
between sp3 hybrid orbital is 109.5° as shown
in Fig. 4.12.

Fig.4.13 Formation of NH3 molecule

In case of H2O molecule, the four oxygen

orbitals (one 2s and three 2p) undergo sp3
hybridisation forming four sp3 hybrid orbitals
out of which two contain one electron each and
the other two contain a pair of electrons. These
σ four sp3 hybrid orbitals acquire a tetrahedral
geometry, with two corners occupied by
σ σ
hydrogen atoms while the other two by the
lone pairs. The bond angle in this case is
σ reduced to 104.5° from 109.5° (Fig. 4.14)
and the molecule thus acquires a V-shape or
angular geometry.

Fig.4.12 Formation of sp 3 hybrids by the

combination of s, px , py and pz atomic
orbitals of carbon and the formation of
CH4 molecule

The structure of NH3 and H2O molecules

can also be explained with the help of sp3
hybridisation. In NH3, the valence shell (outer)
electronic configuration of nitrogen in the Fig.4.14 Formation of H2O molecule

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4.6.2 Other Examples of sp3, sp2 and sp used for making sp2–s sigma bond with two
Hybridisation hydrogen atoms. The unhybridised orbital (2px
sp Hybridisation in C2H6 molecule: In
3 or 2py) of one carbon atom overlaps sidewise
ethane molecule both the carbon atoms with the similar orbital of the other carbon
assume sp3 hybrid state. One of the four atom to form weak π bond, which consists of
sp3 hybrid orbitals of carbon atom overlaps two equal electron clouds distributed above
axially with similar orbitals of other atom to and below the plane of carbon and hydrogen
form sp3-sp3 sigma bond while the other three atoms.
hybrid orbitals of each carbon atom are used
in forming sp3–s sigma bonds with hydrogen Thus, in ethene molecule, the carbon-
atoms as discussed in section 4.6.1(iii). carbon bond consists of one sp2–sp2 sigma
Therefore in ethane C–C bond length is 154 bond and one pi (π ) bond between p orbitals
pm and each C–H bond length is 109 pm. which are not used in the hybridisation and
are perpendicular to the plane of molecule; the
sp2 Hybridisation in C2H4: In the formation
bond length 134 pm. The C–H bond is sp2–s
of ethene molecule, one of the sp2 hybrid
orbitals of carbon atom overlaps axially with sigma with bond length 108 pm. The H–C–H
sp2 hybridised orbital of another carbon atom bond angle is 117.6° while the H–C–C angle
to form C–C sigma bond. While the other two is 121°. The formation of sigma and pi bonds
sp2 hybrid orbitals of each carbon atom are in ethene is shown in Fig. 4.15.

Fig. 4.15 Formation of sigma and pi bonds in ethene

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sp Hybridisation in C2H2 : In the formation 4.6.3 Hybridisation of Elements

of ethyne molecule, both the carbon atoms involving d Orbitals
undergo sp-hybridisation having two The elements present in the third period
unhybridised orbital i.e., 2py and 2px. contain d orbitals in addition to s and p
orbitals. The energy of the 3d orbitals are
One sp hybrid orbital of one carbon atom
comparable to the energy of the 3s and 3p
overlaps axially with sp hybrid orbital of the
orbitals. The energy of 3d orbitals are also
other carbon atom to form C–C sigma bond, comparable to those of 4s and 4p orbitals.
while the other hybridised orbital of each As a consequence the hybridisation involving
carbon atom overlaps axially with the half either 3s, 3p and 3d or 3d, 4s and 4p is
filled s orbital of hydrogen atoms forming possible. However, since the difference in
σ bonds. Each of the two unhybridised p energies of 3p and 4s orbitals is significant, no
orbitals of both the carbon atoms overlaps hybridisation involving 3p, 3d and 4s orbitals
sidewise to form two π bonds between the is possible.
carbon atoms. So the triple bond between the The important hybridisation schemes
two carbon atoms is made up of one sigma involving s, p and d orbitals are summarised
and two pi bonds as shown in Fig. 4.16. below:

Shape of
Hybridisation Atomic
molecules/ Examples
type orbitals
ions

Square dsp2 d+s+p(2) [Ni(CN)4]2–,

planar [Pt(Cl)4]2–
Trigonal sp3d s+p(3)+d PF5, PCl5
bipyramidal
Square sp3d2 s+p(3)+d(2) BrF5
pyramidal
Octahedral sp3d2 s+p(3)+d(2) SF6, [CrF6]3–
d2sp3 d(2)+s+p(3) [Co(NH3)6]3+

(i) Formation of PCl5 (sp3d hybridisation):

The ground state and the excited state outer
electronic configurations of phosphorus
(Z=15) are represented below.

Fig.4.16 Formation of sigma and pi bonds in sp3d hybrid orbitals filled by electron pairs
ethyne donated by five Cl atoms.

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Now the five orbitals (i.e., one s, three six sp3d2 hybrid orbitals overlap with singly
p and one d orbitals) are available for occupied orbitals of fluorine atoms to form
hybridisation to yield a set of five sp3d hybrid six S–F sigma bonds. Thus SF6 molecule has
orbitals which are directed towards the five a regular octahedral geometry as shown in
corners of a trigonal bipyramidal as depicted Fig. 4.18.
in the Fig. 4.17.

sp3d2 hybridisation

Fig. 4.17 Trigonal bipyramidal geometry of PCl5

molecule

It should be noted that all the bond angles

in trigonal bipyramidal geometry are not
equivalent. In PCl5 the five sp3d orbitals of
phosphorus overlap with the singly occupied
p orbitals of chlorine atoms to form five P–Cl
sigma bonds. Three P–Cl bond lie in one
plane and make an angle of 120° with each
other; these bonds are termed as equatorial
Fig. 4.18 Octahedral geometry of SF6 molecule
bonds. The remaining two P–Cl bonds–one
lying above and the other lying below the
equatorial plane, make an angle of 90° with 4.7 Molecular Orbital Theory
the plane. These bonds are called axial bonds. Molecular orbital (MO) theory was developed
As the axial bond pairs suffer more repulsive by F. Hund and R.S. Mulliken in 1932. The
interaction from the equatorial bond pairs, salient features of this theory are :
therefore axial bonds have been found to (i) The electrons in a molecule are present
be slightly longer and hence slightly weaker in the various molecular orbitals as the
than the equatorial bonds; which makes PCl5
electrons of atoms are present in the
molecule more reactive.
various atomic orbitals.
(ii) Formation of SF6 (sp3d2 hybridisation):
In SF6 the central sulphur atom has the (ii) The atomic orbitals of comparable
ground state outer electronic configuration energies and proper symmetry combine
3s23p4. In the exited state the available six to form molecular orbitals.
orbitals i.e., one s, three p and two d are (iii) While an electron in an atomic orbital
singly occupied by electrons. These orbitals is influenced by one nucleus, in a
hybridise to form six new sp 3 d 2 hybrid molecular orbital it is influenced by
orbitals, which are projected towards the six two or more nuclei depending upon the
corners of a regular octahedron in SF6. These number of atoms in the molecule. Thus,

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an atomic orbital is monocentric while ψA and ψB. Mathematically, the formation of

a molecular orbital is polycentric. molecular orbitals may be described by the
(iv) The number of molecular orbital formed linear combination of atomic orbitals that can
is equal to the number of combining take place by addition and by subtraction of
atomic orbitals. When two atomic wave functions of individual atomic orbitals
orbitals combine, two molecular orbitals as shown below :
are formed. One is known as bonding ψMO = ψA + ψB
molecular orbital while the other is Therefore, the two molecular orbitals
called antibonding molecular orbital. σ and σ* are formed as :
(v) The bonding molecular orbital has σ = ψA + ψB
lower energy and hence greater stability σ* = ψA – ψB
than the corresponding antibonding
The molecular orbital σ formed by the
molecular orbital.
addition of atomic orbitals is called the bonding
(vi) Just as the electron probability molecular orbital while the molecular orbital
distribution around a nucleus in an σ* formed by the subtraction of atomic orbital
atom is given by an atomic orbital, the is called antibonding molecular orbital as
electron probability distribution around depicted in Fig. 4.19.
a group of nuclei in a molecule is given
by a molecular orbital.
(vii) The molecular orbitals like atomic
orbitals are filled in accordance with
the aufbau principle obeying the Pauli’s
exclusion principle and the Hund’s rule.

4.7.1 Formation of Molecular Orbitals

Linear Combination of Atomic σ* = ψA – ψB
Orbitals (LCAO)
According to wave mechanics, the atomic ψA ψB
orbitals can be expressed by wave functions
(ψ ’s) which represent the amplitude of the
σ = ψA + ψB
electron waves. These are obtained from
the solution of Schrödinger wave equation.
However, since it cannot be solved for any
system containing more than one electron,
molecular orbitals which are one electron
wave functions for molecules are difficult Fig.4.19 Formation of bonding (σ) and antibonding
to obtain directly from the solution of (σ*) molecular orbitals by the linear
Schrödinger wave equation. To overcome combination of atomic orbitals ψA and
this problem, an approximate method known ψB centered on two atoms A and B
respectively.
as linear combination of atomic orbitals
(LCAO) has been adopted.
Qualitatively, the formation of molecular
Let us apply this method to the orbitals can be understood in terms of the
homonuclear diatomic hydrogen molecule. constructive or destructive interference of the
Consider the hydrogen molecule consisting electron waves of the combining atoms. In the
of two atoms A and B. Each hydrogen atom formation of bonding molecular orbital, the
in the ground state has one electron in 1s two electron waves of the bonding atoms
orbital. The atomic orbitals of these atoms reinforce each other due to constructive
may be represented by the wave functions interference while in the formation of

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antibonding molecular orbital, the electron as the molecular axis. It is important to note
waves cancel each other due to destructive that atomic orbitals having same or nearly
interference. As a result, the electron density in the same energy will not combine if they do
a bonding molecular orbital is located between not have the same symmetry. For example,
the nuclei of the bonded atoms because of 2pz orbital of one atom can combine with 2pz
which the repulsion between the nuclei is very orbital of the other atom but not with the
less while in case of an antibonding molecular 2px or 2py orbitals because of their different
orbital, most of the electron density is located symmetries.
away from the space between the nuclei. 3. The combining atomic orbitals must
Infact, there is a nodal plane (on which the overlap to the maximum extent. Greater
electron density is zero) between the nuclei the extent of overlap, the greater will be the
and hence the repulsion between the nuclei is electron-density between the nuclei of a
high. Electrons placed in a bonding molecular molecular orbital.
orbital tend to hold the nuclei together and
stabilise a molecule. Therefore, a bonding 4.7.3 Types of Molecular Orbitals
molecular orbital always possesses lower Molecular orbitals of diatomic molecules are
energy than either of the atomic orbitals that designated as σ (sigma), π (pi), δ (delta), etc.
have combined to form it. In contrast, the In this nomenclature, the sigma ( )
electrons placed in the antibonding molecular molecular orbitals are symmetrical around
orbital destabilise the molecule. This is the bond-axis while pi ( ) molecular orbitals
because the mutual repulsion of the electrons are not symmetrical. For example, the linear
in this orbital is more than the attraction combination of 1s orbitals centered on two
between the electrons and the nuclei, which nuclei produces two molecular orbitals which
causes a net increase in energy. are symmetrical around the bond-axis. Such
It may be noted that the energy of the molecular orbitals are of the σ type and are
antibonding orbital is raised above the designated as σ1s and σ*1s [Fig. 4.20(a), page
energy of the parent atomic orbitals that 124]. If internuclear axis is taken to be in
have combined and the energy of the bonding the z-direction, it can be seen that a linear
orbital has been lowered than the parent combination of 2pz- orbitals of two atoms
orbitals. The total energy of two molecular also produces two sigma molecular orbitals
orbitals, however, remains the same as that designated as 2pz and *2pz. [Fig. 4.20(b)]
of two original atomic orbitals. Molecular orbitals obtained from 2px and
4.7.2 Conditions for the Combination of 2py orbitals are not symmetrical around the
Atomic Orbitals bond axis because of the presence of positive
The linear combination of atomic orbitals to lobes above and negative lobes below the
form molecular orbitals takes place only if the molecular plane. Such molecular orbitals,
following conditions are satisfied: are labelled as π and =π * [Fig. 4.20(c)]. A
π bonding MO has larger electron density
1. The combining atomic orbitals must
above and below the inter-nuclear axis. The
have the same or nearly the same energy.
π* antibonding MO has a node between the
This means that 1s orbital can combine with
nuclei.
another 1s orbital but not with 2s orbital
because the energy of 2s orbital is appreciably 4.7.4 Energy Level Diagram for Molecular
higher than that of 1s orbital. This is not true Orbitals
if the atoms are very different. We have seen that 1s atomic orbitals on two
2. The combining atomic orbitals must atoms form two molecular orbitals designated
have the same symmetry about the as σ1s and σ*1s. In the same manner, the 2s
molecular axis. By convention z-axis is taken and 2p atomic orbitals (eight atomic orbitals

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 128 chemistry

Fig. 4.20 Contours and energies of bonding and antibonding molecular orbitals formed through
combinations of (a) 1s atomic orbitals; (b) 2pz atomic orbitals and (c) 2px atomic orbitals.

on two atoms) give rise to the following eight The energy levels of these molecular
molecular orbitals: orbitals have been determined experimentally
Antibonding MOs σ∗2s σ∗2pz π∗2px π∗2py from spectroscopic data for homonuclear
diatomic molecules of second row elements
Bonding MOs σ2s σ2pz π2px π2py
of the periodic table. The increasing order of

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energies of various molecular orbitals for O2 The rules discussed above regarding the
and F2 is given below: stability of the molecule can be restated in
terms of bond order as follows: A positive bond
1s <  ∗1s <  2s <  ∗2s < 2pz < (π 2px=π 2py)
order (i.e., Nb > Na) means a stable molecule
< (π ∗2px= π∗ 2py) <  ∗2pz while a negative (i.e., Nb<Na) or zero (i.e.,
However, this sequence of energy levels N b = N a) bond order means an unstable
of molecular orbitals is not correct for the molecule.
remaining molecules Li2, Be2, B2, C2, N2. For Nature of the bond
instance, it has been observed experimentally Integral bond order values of 1, 2 or 3
that for molecules such as B2, C2, N2, etc. correspond to single, double or triple bonds
the increasing order of energies of various respectively as studied in the classical
molecular orbitals is concept.
1s <  ∗1s < 2s <  ∗2s < (π 2 px = π 2 py) Bond-length
< 2pz < (π ∗2px =π∗2py) <  ∗2pz The bond order between two atoms in a
The important characteristic feature molecule may be taken as an approximate
of this order is that the energy of 2p z measure of the bond length. The bond length
molecular orbital is higher than that decreases as bond order increases.
of 2px and 2py molecular orbitals. Magnetic nature
4.7.5 Electronic Configuration and If all the molecular orbitals in a molecule are
Molecular Behaviour doubly occupied, the substance is diamagnetic
The distribution of electrons among various (repelled by magnetic field). However if one or
molecular orbitals is called the electronic more molecular orbitals are singly occupied it
configuration of the molecule. From the is paramagnetic (attracted by magnetic field),
electronic configuration of the molecule, it is e.g., O2 molecule.
possible to get important information about 4.8 BONDING IN SOME HOMONUCLEAR
the molecule as discussed below. DIATOMIC MOLECULES
Stability of Molecules: If Nb is the number In this section we shall discuss bonding in
of electrons occupying bonding orbitals and some homonuclear diatomic molecules.
Na the number occupying the antibonding
1. Hydrogen molecule (H2 ): It is formed by
orbitals, then
the combination of two hydrogen atoms. Each
(i) the molecule is stable if Nb is greater hydrogen atom has one electron in 1s orbital.
than Na, and Therefore, in all there are two electrons in
(ii) the molecule is unstable if Nb is less hydrogen molecule which are present in σ1s
than Na. molecular orbital. So electronic configuration
of hydrogen molecule is
In (i) more bonding orbitals are occupied
and so the bonding influence is stronger and a H2 : (σ1s)2
stable molecule results. In (ii) the antibonding The bond order of H2 molecule can be
influence is stronger and therefore the calculated as given below:
molecule is unstable. N b  Na 2  0
Bond order Bond order =  1
2 2
Bond order (b.o.) is defined as one half the This means that the two hydrogen atoms
difference between the number of electrons are bonded together by a single covalent bond.
present in the bonding and the antibonding The bond dissociation energy of hydrogen
orbitals i.e., molecule has been found to be 438 kJ mol–1
Bond order (b.o.) = ½ (Nb–Na) and bond length equal to 74 pm. Since no

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unpaired electron is present in hydrogen vapour phase. It is important to note that

molecule, therefore, it is diamagnetic. double bond in C2 consists of both pi bonds
2. Helium molecule (He2 ): The electronic because of the presence of four electrons in
configuration of helium atom is 1s2. Each two pi molecular orbitals. In most of the other
helium atom contains 2 electrons, therefore, molecules a double bond is made up of a
in He2 molecule there would be 4 electrons. sigma bond and a pi bond. In a similar fashion
These electrons will be accommodated in the bonding in N2 molecule can be discussed.
σ1s and σ*1s molecular orbitals leading to 5. Oxygen molecule (O2 ): The electronic
electronic configuration: configuration of oxygen atom is 1s2 2s2 2p4.
Each oxygen atom has 8 electrons, hence,
He2 : (σ1s)2 (σ*1s)2 in O2 molecule there are 16 electrons. The
Bond order of He2 is ½(2 – 2) = 0 electronic configuration of O 2 molecule,
therefore, is
He2 molecule is therefore unstable and
does not exist.
O 2 : (1s) 2 ( ∗1s) 2 ( 2s) 2 ( ∗ 2s) 2 (2p z) 2
Similarly, it can be shown that Be2 molecule (π2px2 ≡ π2py2) (π∗2p1x ≡ π ∗2py1)
(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 also does not exist.
3. Lithium molecule (Li2 ): The electronic
configuration of lithium is 1s2, 2s1. There O2 :
are six electrons in Li 2 . The electronic
configuration of Li2 molecule, therefore, is From the electronic configuration of O2
molecule it is clear that ten electrons are
Li2 : (σ1s)2 (σ*1s)2 (σ2s)2 present in bonding molecular orbitals and six
The above configuration is also written electrons are present in antibonding molecular
as KK(σ2s)2 where KK represents the closed orbitals. Its bond order, therefore, is
K shell structure (σ1s)2 (σ*1s)2.
From the electronic configuration of Li2 Bond order = [Nb – Na] = [10 – 6] =2
molecule it is clear that there are four electrons
present in bonding molecular orbitals and two So in oxygen molecule, atoms are held
electrons present in antibonding molecular by a double bond. Moreover, it may be noted
orbitals. Its bond order, therefore, is ½ (4 – that it contains two unpaired electrons in
2) = 1. It means that Li2 molecule is stable π ∗2px and π ∗2py molecular orbitals, therefore,
and since it has no unpaired electrons it O 2 molecule should be paramagnetic,
a prediction that corresponds to
should be diamagnetic.  Indeed diamagnetic
experimental observation. In this way, the
Li 2 molecules are known to exist in the
theory successfully explains the paramagnetic
vapour phase.
nature of oxygen.
4. Carbon molecule (C2 ): The electronic
configuration of carbon is 1s2 2s2 2p2. There Similarly, the electronic configurations
of other homonuclear diatomic molecules of []
are twelve electrons in C2. The electronic
the second row of the periodic table can be
configuration of C2 molecule, therefore, is
written. In Fig. 4.21 are given the molecular
C2 : (1s)2 ( ∗1s)2 ( ∗ 2s)2 (π2p2x = π2p2y) orbital occupancy and molecular properties
for B2 through Ne2. The sequence of MOs and
or KK (2s)2 ( ∗ 2s)2 (π2p2x = π2p2y) their electron population are shown. The bond
The bond order of C2 is ½ (8 – 4) = 2 energy, bond length, bond order, magnetic
and C2 should be diamagnetic. Diamagnetic properties and valence electron configuration
C2 molecules have indeed been detected in appear below the orbital diagrams.

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Fig. 4.21 MO occupancy and molecular properties for B2 through Ne2.

4.9 Hydrogen Bonding Hydrogen bond is represented by a dotted

Nitrogen, oxygen and fluorine are the highly line (– – –) while a solid line represents the
electronegative elements. When they are covalent bond. Thus, hydrogen bond can be
attached to a hydrogen atom to form covalent defined as the attractive force which binds
bond, the electrons of the covalent bond are hydrogen atom of one molecule with the
shifted towards the more electronegative electronegative atom (F, O or N) of another
atom. This partially positively charged molecule.
hydrogen atom forms a bond with the other
4.9.1 Cause of Formation of Hydrogen
more electronegative atom. This bond is Bond
known as hydrogen bond and is weaker
than the covalent bond. For example, in HF When hydrogen is bonded to strongly
molecule, the hydrogen bond exists between electronegative element ‘X’, the electron pair
hydrogen atom of one molecule and fluorine shared between the two atoms moves far
atom of another molecule as depicted below : away from hydrogen atom. As a result the
hydrogen atom becomes highly electropositive
– – – Hδ+–Fδ– – – –Hδ+ – Fδ– – – – Hδ+ – Fδ– with respect to the other atom ‘X’. Since
Here, hydrogen bond acts as a bridge between there is displacement of electrons towards
two atoms which holds one atom by covalent X, the hydrogen acquires fractional positive
bond and the other by hydrogen bond. charge (δ +) while ‘X’ attain fractional negative

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charge (δ–). This results in the formation of a H-bond in case of HF molecule, alcohol or
polar molecule having electrostatic force of water molecules, etc.
attraction which can be represented as: (2) Intramolecular hydrogen bond : It is
formed when hydrogen atom is in between
Hδ+ – Xδ– – – – Hδ+ – Xδ– – – – Hδ+ – Xδ– the two highly electronegative (F, O, N)
The magnitude of H-bonding depends atoms present within the same molecule. For
on the physical state of the compound. It is example, in o-nitrophenol the hydrogen is in
maximum in the solid state and minimum in between the two oxygen atoms.
the gaseous state. Thus, the hydrogen bonds
have strong influence on the structure and
properties of the compounds.
4.9.2 Types of H-Bonds
There are two types of H-bonds
(i) Intermolecular hydrogen bond
(ii) Intramolecular hydrogen bond
(1) Intermolecular hydrogen bond : It is
formed between two different molecules of the Fig. 4.22 Intramolecular hydrogen bonding in
same or different compounds. For example, o-nitrophenol molecule

SUMMARY

Kössel’s first insight into the mechanism of formation of electropositive and electronegative
ions related the process to the attainment of noble gas configurations by the respective ions.
Electrostatic attraction between ions is the cause for their stability. This gives the concept
of electrovalency.

The first description of covalent bonding was provided by Lewis in terms of the sharing
of electron pairs between atoms and he related the process to the attainment of noble gas
configurations by reacting atoms as a result of sharing of electrons. The Lewis dot symbols
show the number of valence electrons of the atoms of a given element and Lewis dot structures
show pictorial representations of bonding in molecules.
An ionic compound is pictured as a three-dimensional aggregation of positive and negative
ions in an ordered arrangement called the crystal lattice. In a crystalline solid there is a
charge balance between the positive and negative ions. The crystal lattice is stabilized by
the enthalpy of lattice formation.
While a single covalent bond is formed by sharing of an electron pair between two atoms,
multiple bonds result from the sharing of two or three electron pairs. Some bonded atoms
have additional pairs of electrons not involved in bonding. These are called lone-pairs of
electrons. A Lewis dot structure shows the arrangement of bonded pairs and lone pairs around
each atom in a molecule. Important parameters, associated with chemical bonds, like:
bond length, bond angle, bond enthalpy, bond order and bond polarity have significant
effect on the properties of compounds.
A number of molecules and polyatomic ions cannot be described accurately by a single
Lewis structure and a number of descriptions (representations) based on the same skeletal
structure are written and these taken together represent the molecule or ion. This is a very
important and extremely useful concept called resonance. The contributing structures
or canonical forms taken together constitute the resonance hybrid which represents the
molecule or ion.

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 Chemical Bonding And Molecular Structure 133

The VSEPR model used for predicting the geometrical shapes of molecules is based on
the assumption that electron pairs repel each other and, therefore, tend to remain as far
apart as possible. According to this model, molecular geometry is determined by repulsions
between lone pairs and lone pairs; lone pairs and bonding pairs and bonding pairs and bonding
pairs. The order of these repulsions being : lp-lp > lp-bp > bp-bp
The valence bond (VB) approach to covalent bonding is basically concerned with the
energetics of covalent bond formation about which the Lewis and VSEPR models are silent.
Basically the VB theory discusses bond formation in terms of overlap of orbitals. For example
the formation of the H2 molecule from two hydrogen atoms involves the overlap of the 1s
orbitals of the two H atoms which are singly occupied. It is seen that the potential energy
of the system gets lowered as the two H atoms come near to each other. At the equilibrium
inter-nuclear distance (bond distance) the energy touches a minimum. Any attempt to bring
the nuclei still closer results in a sudden increase in energy and consequent destabilization
of the molecule. Because of orbital overlap the electron density between the nuclei increases
which helps in bringing them closer. It is however seen that the actual bond enthalpy and
bond length values are not obtained by overlap alone and other variables have to be taken
into account.
For explaining the characteristic shapes of polyatomic molecules Pauling introduced the
concept of hybridisation of atomic orbitals. sp, sp2, sp3 hybridizations of atomic orbitals
of Be, B, C, N and O are used to explain the formation and geometrical shapes of molecules
like BeCl2, BCl3, CH4, NH3 and H2O. They also explain the formation of multiple bonds in
molecules like C2H2 and C2H4.
The molecular orbital (MO) theory describes bonding in terms of the combination and
arrangment of atomic orbitals to form molecular orbitals that are associated with the molecule
as a whole. The number of molecular orbitals are always equal to the number of atomic
orbitals from which they are formed. Bonding molecular orbitals increase electron density
between the nuclei and are lower in energy than the individual atomic orbitals. Antibonding
molecular orbitals have a region of zero electron density between the nuclei and have more
energy than the individual atomic orbitals.
The electronic configuration of the molecules is written by filling electrons in the molecular
orbitals in the order of increasing energy levels. As in the case of atoms, the Pauli exclusion
principle and Hund’s rule are applicable for the filling of molecular orbitals. Molecules are
said to be stable if the number of elctrons in bonding molecular orbitals is greater than that
in antibonding molecular orbitals.
Hydrogen bond is formed when a hydrogen atom finds itself between two highly
electronegative atoms such as F, O and N. It may be intermolecular (existing between two
or more molecules of the same or different substances) or intramolecular (present within
the same molecule). Hydrogen bonds have a powerful effect on the structure and properties
of many compounds.

EXERCISES

4.1 Explain the formation of a chemical bond.

4.2 Write Lewis dot symbols for atoms of the following elements : Mg, Na, B, O, N, Br.
4.3 Write Lewis symbols for the following atoms and ions:
S and S2–; Al and Al3+; H and H–
4.4 Draw the Lewis structures for the following molecules and ions :
2−
H2S, SiCl4, BeF2, CO3 , HCOOH
4.5 Define octet rule. Write its significance and limitations.

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 134 chemistry

4.6 Write the favourable factors for the formation of ionic bond.
4.7 Discuss the shape of the following molecules using the VSEPR model:
BeCl2, BCl3, SiCl4, AsF5, H2S, PH3
4.8 Although geometries of NH3 and H2O molecules are distorted tetrahedral, bond angle
in water is less than that of ammonia. Discuss.
4.9 How do you express the bond strength in terms of bond order ?
4.10 Define the bond length.
2−
4.11 Explain the important aspects of resonance with reference to the CO3 ion.
4.12 H3PO3 can be represented by structures 1 and 2 shown below. Can these two
structures be taken as the canonical forms of the resonance hybrid representing
H3PO3 ? If not, give reasons for the same.

−
4.13 Write the resonance structures for SO3, NO2 and NO3 .
4.14 Use Lewis symbols to show electron transfer between the following atoms to form
cations and anions : (a) K and S (b) Ca and O (c) Al and N.
4.15 Although both CO2 and H2O are triatomic molecules, the shape of H2O molecule is
bent while that of CO2 is linear. Explain this on the basis of dipole moment.
4.16 Write the significance/applications of dipole moment.
4.17 Define electronegativity. How does it differ from electron gain enthalpy ?
4.18 Explain with the help of suitable example polar covalent bond.
4.19 Arrange the bonds in order of increasing ionic character in the molecules: LiF, K2O,
N2, SO2 and ClF3.
4.20 The skeletal structure of CH3COOH as shown below is correct, but some of the bonds
are shown incorrectly. Write the correct Lewis structure for acetic acid.

4.21 Apart from tetrahedral geometry, another possible geometry for CH4 is square planar
with the four H atoms at the corners of the square and the C atom at its centre.
Explain why CH4 is not square planar ?
4.22 Explain why BeH2 molecule has a zero dipole moment although the Be–H bonds are
polar.
4.23 Which out of NH3 and NF3 has higher dipole moment and why ?
4.24 What is meant by hybridisation of atomic orbitals? Describe the shapes of sp, sp2,
sp3 hybrid orbitals.
4.25 Describe the change in hybridisation (if any) of the Al atom in the following reaction.
AlCl 3  Cl   AlCl 4

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 Chemical Bonding And Molecular Structure 135

4.26 Is there any change in the hybridisation of B and N atoms as a result of the following
reaction?

4.27 Draw diagrams showing the formation of a double bond and a triple bond between
carbon atoms in C2H4 and C2H2 molecules.
4.28 What is the total number of sigma and pi bonds in the following molecules?
(a) C2H2 (b) C2H4
4.29 Considering x-axis as the internuclear axis which out of the following will
not form a sigma bond and why? (a) 1s and 1s (b) 1s and 2px; (c) 2py and 2py
(d) 1s and 2s.
4.30 Which hybrid orbitals are used by carbon atoms in the following molecules?
CH3–CH3; (b) CH3–CH=CH2; (c) CH3-CH2-OH; (d) CH3-CHO (e) CH3COOH
4.31 What do you understand by bond pairs and lone pairs of electrons? Illustrate by
giving one exmaple of each type.
4.32 Distinguish between a sigma and a pi bond.
4.33 Explain the formation of H2 molecule on the basis of valence bond theory.
4.34 Write the important conditions required for the linear combination of atomic orbitals
to form molecular orbitals.
4.35 Use molecular orbital theory to explain why the Be2 molecule does not exist.
4.36 Compare the relative stability of the following species and indicate their magnetic
properties;
2−
(superoxide), O2 (peroxide)
4.37 Write the significance of a plus and a minus sign shown in representing the orbitals.
4.38 Describe the hybridisation in case of PCl5. Why are the axial bonds longer as compared
to equatorial bonds?
4.39 Define hydrogen bond. Is it weaker or stronger than the van der Waals forces?
4.40 What is meant by the term bond order? Calculate the bond order of : N2, O2, O2+
and O2–.

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 Unit 5

Thermodynamics

It is the only physical theory of universal content concerning

which I am convinced that, within the framework of the
applicability of its basic concepts, it will never be overthrown.

After studying this Unit, you will be Albert Einstein

able to
• explain the terms : system and
surroundings;
• discriminate between close, open
and isolated systems;
Chemical energy stored by molecules can be released as
• explain internal energy, work and
heat; heat during chemical reactions when a fuel like methane,
• state first law of thermodynamics cooking gas or coal burns in air. The chemical energy may
and express it mathematically; also be used to do mechanical work when a fuel burns
• calculate energy changes as in an engine or to provide electrical energy through a
work and heat contributions in galvanic cell like dry cell. Thus, various forms of energy
chemical systems;
are interrelated and under certain conditions, these may
• explain state functions: U, H.
be transformed from one form into another. The study
• correlate ∆U and ∆H;
of these energy transformations forms the subject matter
• measure experimentally ∆U and
∆H; of thermodynamics. The laws of thermodynamics deal
• define standard states for ∆H; with energy changes of macroscopic systems involving
• calculate enthalpy changes for a large number of molecules rather than microscopic
various types of reactions; systems containing a few molecules. Thermodynamics is
• state and apply Hess’s law of not concerned about how and at what rate these energy
constant heat summation; transformations are carried out, but is based on initial and
• differentiate between extensive final states of a system undergoing the change. Laws of
and intensive properties;
thermodynamics apply only when a system is in equilibrium
• define spontaneous and non-
spontaneous processes;
or moves from one equilibrium state to another equilibrium
• explain entropy as a
state. Macroscopic properties like pressure and temperature
thermodynamic state function do not change with time for a system in equilibrium state.
and apply it for spontaneity; In this unit, we would like to answer some of the important
• explain Gibbs energy change (∆G); questions through thermodynamics, like:
and
How do we determine the energy changes involved in a
• establish relationship between
∆G and spontaneity, ∆G and chemical reaction/process? Will it occur or not?
equilibrium constant. What drives a chemical reaction/process?
To what extent do the chemical reactions proceed?

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 THERMODYNAMICS 137

5.1 Thermodynamic terms the system from the surroundings is called

We are interested in chemical reactions and boundary. This is designed to allow us to
the energy changes accompanying them. For control and keep track of all movements of
this we need to know certain thermodynamic matter and energy in or out of the system.
terms. These are discussed below.
5.1.2 Types of the System
5.1.1 The System and the Surroundings We, further classify the systems according
A system in thermodynamics refers to that to the movements of matter and energy in or
part of universe in which observations are out of the system.
made and remaining universe constitutes
the surroundings. The surroundings include 1. Open System
everything other than the system. System In an open system, there is exchange of energy
and the surroundings together constitute the and matter between system and surroundings
universe. [Fig. 5.2 (a)]. The presence of reactants in an
The universe = The system + The surroundings open beaker is an example of an open system*.
Here the boundary is an imaginary surface
However, the entire universe other than enclosing the beaker and reactants.
the system is not affected by the changes
taking place in the system. Therefore, for all 2. Closed System
practical purposes, the surroundings are that In a closed system, there is no exchange of
portion of the remaining universe which can matter, but exchange of energy is possible
interact with the system. Usually, the region between system and the surroundings
of space in the neighbourhood of the system [Fig. 5.2 (b)]. The presence of reactants in a
constitutes its surroundings. closed vessel made of conducting material
For example, if we are studying the e.g., copper or steel is an example of a closed
reaction between two substances A and B system.
kept in a beaker, the beaker containing the
reaction mixture is the system and the room
where the beaker is kept is the surroundings
(Fig. 5.1).

Fig. 5.1 System and the surroundings

Note that the system may be defined
by physical boundaries, like beaker or test
tube, or the system may simply be defined
by a set of Cartesian coordinates specifying
a particular volume in space. It is necessary
to think of the system as separated from the
surroundings by some sort of wall which may
be real or imaginary. The wall that separates Fig. 5.2 Open, closed and isolated systems.
* We could have chosen only the reactants as system then walls of the beakers will act as boundary.

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 138 chemIstry

3. Isolated System a quantity which represents the total energy

In an isolated system, there is no exchange of the system. It may be chemical, electrical,
of energy or matter between the system and mechanical or any other type of energy you
the surroundings [Fig. 5.2 (c)]. The presence may think of, the sum of all these is the energy
of reactants in a thermos flask or any other of the system. In thermodynamics, we call it
closed insulated vessel is an example of an the internal energy, U of the system, which
isolated system. may change, when
• heat passes into or out of the system,
5.1.3 The State of the System • work is done on or by the system,
The system must be described in order to
• matter enters or leaves the system.
make any useful calculations by specifying
quantitatively each of the properties such as These systems are classified accordingly
its pressure (p), volume (V), and temperature as you have already studied in section 5.1.2.
(T ) as well as the composition of the system.
(a) Work
We need to describe the system by specifying
it before and after the change. You would Let us first examine a change in internal energy
recall from your Physics course that the by doing work. We take a system containing
state of a system in mechanics is completely some quantity of water in a thermos flask
specified at a given instant of time, by the or in an insulated beaker. This would not
position and velocity of each mass point of allow exchange of heat between the system
the system. In thermodynamics, a different and surroundings through its boundary and
and much simpler concept of the state of a we call this type of system as adiabatic. The
system is introduced. It does not need detailed manner in which the state of such a system
knowledge of motion of each particle because, may be changed will be called adiabatic
we deal with average measurable properties of process. Adiabatic process is a process in
the system. We specify the state of the system which there is no transfer of heat between
by state functions or state variables. the system and surroundings. Here, the wall
The state of a thermodynamic system is separating the system and the surroundings
described by its measurable or macroscopic is called the adiabatic wall (Fig. 5.3).
(bulk) properties. We can describe the state
of a gas by quoting its pressure (p), volume
(V), temperature (T ), amount (n) etc. Variables
like p, V, T are called state variables or state
functions because their values depend only
on the state of the system and not on how it
is reached. In order to completely define the
state of a system it is not necessary to define
all the properties of the system; as only a
certain number of properties can be varied
independently. This number depends on the
nature of the system. Once these minimum
number of macroscopic properties are fixed, Fig. 5.3 An adiabatic system which does not
others automatically have definite values. permit the transfer of heat through its
The state of the surroundings can never boundary.
be completely specified; fortunately it is not Let us bring the change in the internal
necessary to do so. energy of the system by doing some work on
it. Let us call the initial state of the system
5.1.4 The Internal Energy as a State as state A and its temperature as TA. Let
Function the internal energy of the system in state A
When we talk about our chemical system be called UA. We can change the state of the
losing or gaining energy, we need to introduce system in two different ways.

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 THERMODYNAMICS 139

One way: We do some mechanical work, say the route taken. Volume of water in a pond, for
1 kJ, by rotating a set of small paddles and example, is a state function, because change
thereby churning water. Let the new state in volume of its water is independent of the
be called B state and its temperature, as route by which water is filled in the pond,
TB. It is found that TB > TA and the change either by rain or by tubewell or by both.
in temperature, ∆T = TB–TA. Let the internal (b) Heat
energy of the system in state B be UB and the
change in internal energy, ∆U =UB– UA. We can also change the internal energy
of a system by transfer of heat from the
Second way: We now do an equal amount
surroundings to the system or vice-versa
(i.e., 1kJ) electrical work with the help of an
immersion rod and note down the temperature without expenditure of work. This exchange
change. We find that the change in temperature of energy, which is a result of temperature
is same as in the earlier case, say, TB – TA. difference is called heat, q. Let us consider
bringing about the same change in temperature
In fact, the experiments in the above (the same initial and final states as before
manner were done by J. P. Joule between in section 5.1.4 (a) by transfer of heat
1840–50 and he was able to show that a through thermally conducting walls instead
given amount of work done on the system, of adiabatic walls (Fig. 5.4).
no matter how it was done (irrespective of
path) produced the same change of state, as
measured by the change in the temperature
of the system.
So, it seems appropriate to define a
quantity, the internal energy U, whose value
is characteristic of the state of a system,
whereby the adiabatic work, wad required to
bring about a change of state is equal to the
difference between the value of U in one state
and that in another state, ∆U i.e.,
∆U =U2 –U1= wad
Fig. 5.4 A system which allows heat transfer
Therefore, internal energy, U, of the through its boundary.
system is a state function.
By conventions of IUPAC in chemical We take water at temperature, TA in a
thermodynamics. The positive sign expresses container having thermally conducting walls,
that wad is positive when work is done on the say made up of copper and enclose it in a
system and the internal energy of system huge heat reservoir at temperature, TB. The
increases. Similarly, if the work is done by the heat absorbed by the system (water), q can be
system, wad will be negative because internal measured in terms of temperature difference,
energy of the system decreases. TB – TA. In this case change in internal energy,
∆U = q, when no work is done at constant
Can you name some other familiar state
volume.
functions? Some of other familiar state
functions are V, p, and T. For example, if we By conventions of IUPAC in chemical
bring a change in temperature of the system thermodynamics. The q is positive, when heat
from 25°C to 35°C, the change in temperature is transferred from the surroundings to the
is 35°C–25°C = +10°C, whether we go straight system and the internal energy of the system
up to 35°C or we cool the system for a few increases and q is negative when heat is
degrees, then take the system to the final transferred from system to the surroundings
temperature. Thus, T is a state function and resulting in decrease of the internal energy of
the change in temperature is independent of the system.
* Earlier negative sign was assigned when the work is done on the system and positive sign when the work is done by the
system. This is still followed in physics books, although IUPAC has recommended the use of new sign convention.

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 140 chemIstry

(c) The general case

Solution
Let us consider the general case in which
a change of state is brought about both by (i) ∆ U = w ad, wall is adiabatic
doing work and by transfer of heat. We write (ii) ∆ U = – q, thermally conducting
change in internal energy for this case as: walls
∆U = q + w (5.1) (iii) ∆ U = q – w, closed system.

For a given change in state, q and w can 5.2 Applications

vary depending on how the change is carried Many chemical reactions involve the generation
out. However, q +w = ∆U will depend only on of gases capable of doing mechanical work or
initial and final state. It will be independent the generation of heat. It is important for us
of the way the change is carried out. If there to quantify these changes and relate them
is no transfer of energy as heat or as work to the changes in the internal energy. Let us
(isolated system) i.e., if w = 0 and q = 0, then see how!
∆ U = 0.
The equation 5.1 i.e., ∆U = q + w is 5.2.1 Work
mathematical statement of the first law of First of all, let us concentrate on the nature of
thermodynamics, which states that work a system can do. We will consider only
The energy of an isolated system is mechanical work i.e., pressure-volume work.
constant. For understanding pressure-volume
It is commonly stated as the law of conservation work, let us consider a cylinder which
of energy i.e., energy can neither be created contains one mole of an ideal gas fitted with
nor be destroyed. a frictionless piston. Total volume of the gas
is Vi and pressure of the gas inside is p. If
Note: There is considerable difference between
external pressure is pex which is greater than
the character of the thermodynamic property
p, piston is moved inward till the pressure
energy and that of a mechanical property such
as volume. We can specify an unambiguous
(absolute) value for volume of a system in a
particular state, but not the absolute value of
the internal energy. However, we can measure
only the changes in the internal energy, ∆U
of the system.

Problem 5.1
Express the change in internal energy
of a system when
(i) No heat is absorbed by the system
from the surroundings, but work
(w) is done on the system. What
type of wall does the system have ?
(ii) No work is done on the system,
but q amount of heat is taken out
from the system and given to the
surroundings. What type of wall
does the system have?
(iii) w amount of work is done by the Fig. 5.5 (a) Work done on an ideal gas in a
cylinder when it is compressed by
system and q amount of heat is
a constant external pressure, p ex
supplied to the system. What type
(in single step) is equal to the shaded
of system would it be? area.

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 THERMODYNAMICS 141

inside becomes equal to pex. Let this change If the pressure is not constant but
be achieved in a single step and the final changes during the process such that it
volume be V f . During this compression, is always infinitesimally greater than the
suppose piston moves a distance, l and pressure of the gas, then, at each stage of
is cross-sectional area of the piston is A compression, the volume decreases by an
[Fig. 5.5(a)]. infinitesimal amount, dV. In such a case we
then, volume change = l × A = ∆V = (Vf – Vi ) can calculate the work done on the gas by the
We also know, pressure = relation
Vf
Therefore, force on the piston = pex . A
If w is the work done on the system by
w p
Vi
ex dV (5.3)
movement of the piston then
w = force × distance = pex . A .l Here, pex at each stage is equal to (pin + dp)
in case of compression [Fig. 5.5(c)]. In an
= pex . (–∆V) = – pex ∆V = – pex (Vf – Vi ) (5.2)
expansion process under similar conditions,
The negative sign of this expression is the external pressure is always less than the
required to obtain conventional sign for w, pressure of the system i.e., pex = (pin– dp). In
which will be positive. It indicates that in case general case we can write, pex = (pin + dp). Such
of compression work is done on the system. processes are called reversible processes.
Here (Vf – Vi ) will be negative and negative
A process or change is said to be
multiplied by negative will be positive. Hence
reversible, if a change is brought out in such a
the sign obtained for the work will be positive.
way that the process could, at any moment,
If the pressure is not constant at every be reversed by an infinitesimal change.
stage of compression, but changes in number A reversible process proceeds infinitely
of finite steps, work done on the gas will be slowly by a series of equilibrium states
summed over all the steps and will be equal such that system and the surroundings are
to – Σ р ∆V [Fig. 5.5 (b)] always in near equilibrium with each other.

Fig. 5.5 (c) pV-plot when pressure is not constant

Fig. 5.5 (b) pV-plot when pressure is not constant and changes in infinite steps (reversible
and changes in finite steps during conditions) during compression from
compression from initial volume, Vi to initial volume, Vi to final volume, Vf .
final volume, Vf . Work done on the gas Work done on the gas is represented
is represented by the shaded area. by the shaded area.

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 142 chemIstry

Processes other than reversible processes Isothermal and free expansion of an

are known as irreversible processes. ideal gas
In chemistry, we face problems that can For isothermal (T = constant) expansion of
be solved if we relate the work term to the an ideal gas into vacuum; w = 0 since pex = 0.
internal pressure of the system. We can Also, Joule determined experimentally that
relate work to internal pressure of the system q = 0; therefore, ∆U = 0
under reversible conditions by writing
equation 5.3 as follows: Equation 5.1, can be
Vf Vf
expressed for isothermal irreversible and
reversible changes as follows:
w rev   
Vi
pex dV    (p
Vi
in  dp ) dV
1. For isothermal irreversible change
q = – w = pex (Vf – Vi )
Since dp × dV is very small we can write 2. For isothermal reversible change
Vf

w rev    pin dV (5.4) q = – w = nRT ln

Vi

Now, the pressure of the gas (pin which we Vf

can write as p now) can be expressed in terms = 2.303 nRT log V
i
of its volume through gas equation. For n mol For adiabatic change, q = 0,
of an ideal gas i.e., pV =nRT
∆U = wad
nRT
p  Problem 5.2
V
Two litres of an ideal gas at a pressure of 10
Therefore, at constant temperature atm expands isothermally at 25 °C into a
(isothermal process), vacuum until its total volume is 10 litres.
Vf How much heat is absorbed and how
dV Vf
w rev    nRT  nRT ln much work is done in the expansion ?
V Vi
Vi
Solution
Vf We have q = – w = pex (10 – 2) = 0(8) = 0
= – 2.303 nRT log (5.5) No work is done; no heat is absorbed.
Vi
Problem 5.3
Free expansion: Expansion of a gas in
Consider the same expansion, but
vacuum (pex = 0) is called free expansion.
this time against a constant external
No work is done during free expansion of an pressure of 1 atm.
ideal gas whether the process is reversible or
irreversible (equation 5.2 and 5.3). Solution
Now, we can write equation 5.1 in number We have q = – w = pex (8) = 8 litre-atm
of ways depending on the type of processes. Problem 5.4
Let us substitute w = – pex∆V (eq. 5.2) in
Consider the expansion given in problem
equation 5.1, and we get 5.2, for 1 mol of an ideal gas conducted
U  q  pex V reversibly.

If a process is carried out at constant volume Solution
(∆V = 0), then Vf
We have q = – w = 2.303 nRT log
∆U = qV Vs
the subscript V in qV denotes that heat is = 2.303 × 1 × 0.8206 × 298 × log 10
supplied at constant volume. 2

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 THERMODYNAMICS 143

Remember ∆H = qp, heat absorbed by the

= 2.303 x 0.8206 x 298 x log 5 system at constant pressure.
= 2.303 x 0.8206 x 298 x 0.6990
= 393.66 L atm ∆H is negative for exothermic reactions
which evolve heat during the reaction and
∆H is positive for endothermic reactions
5.2.2 Enthalpy, H
which absorb heat from the surroundings.
(a) A Useful New State Function
At constant volume (∆V = 0), ∆U = qV,
We know that the heat absorbed at constant therefore equation 5.8 becomes
volume is equal to change in the internal
∆H = ∆U = qV
energy i.e., ∆U = qV. But most of chemical
reactions are carried out not at constant The difference between ∆H and ∆U is not
volume, but in flasks or test tubes under usually significant for systems consisting
constant atmospheric pressure. We need to of only solids and / or liquids. Solids and
define another state function which may be liquids do not suffer any significant volume
suitable under these conditions. changes upon heating. The difference,
however, becomes significant when gases are
We may write equation (5.1) as
involved. Let us consider a reaction involving
∆U = qp – p∆V at constant pressure, where
gases. If VA is the total volume of the gaseous
qp is heat absorbed by the system and –p ∆V
reactants, VB is the total volume of the gaseous
represent expansion work done by the system.
products, nA is the number of moles of gaseous
Let us represent the initial state by
reactants and nB is the number of moles of
subscript 1 and final state by 2
gaseous products, all at constant pressure
We can rewrite the above equation as and temperature, then using the ideal gas
U2–U1 = qp – p (V2 – V1) law, we write,
On rearranging, we get pVA = nART
qp = (U2 + pV2) – (U1 + pV1) (5.6) and pVB = nBRT
Now we can define another thermodynamic
function, the enthalpy H [Greek word Thus, pVB – pVA = nBRT – nART = (nB–nA)RT
enthalpien, to warm or heat content] as : or p (VB – VA) = (nB – nA) RT
H = U + pV (5.7)
or p ∆V = ∆ngRT (5.9)
so, equation (5.6) becomes
qp= H2 – H1 = ∆H Here, ∆ng refers to the number of moles of
gaseous products minus the number of moles
Although q is a path dependent function,
of gaseous reactants.
H is a state function because it depends on
U, p and V, all of which are state functions. Substituting the value of p∆V from
Therefore, ∆H is independent of path. Hence, equation 5.9 in equation 5.8, we get
qp is also independent of path. ∆H = ∆U + ∆ngRT (5.10)
For finite changes at constant pressure, The equation 5.10 is useful for calculating
we can write equation 5.7 as ∆H from ∆U and vice versa.
∆H = ∆U + ∆pV
Since p is constant, we can write Problem 5.5
∆H = ∆U + p∆V (5.8) If water vapour is assumed to be a
perfect gas, molar enthalpy change for
It is important to note that when heat is vapourisation of 1 mol of water at 1bar
absorbed by the system at constant pressure, and 100°C is 41kJ mol–1. Calculate the
we are actually measuring changes in the internal energy change, when
enthalpy.

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 144 chemIstry

1 mol of water is vapourised at 1 bar

pressure and 100°C.
Solution
(i) The change H2O (l ) → H2O (g)
∆H = ∆U + ∆ngRT Fig. 5.6(a) A gas at volume V and temperature T
or ∆U = ∆H – ∆ngRT, substituting the
values, we get
∆U = 41.00 kJ mol–1 – 1
× 8.3 J mol–1 K–1 × 373 K
= 41.00 kJ mol-1 – 3.096 kJ mol-1
= 37.904 kJ mol–1 Fig. 5.6 (b) Partition, each part having half the
volume of the gas

(b) Extensive and Intensive Properties (c) Heat Capacity

In thermodynamics, a distinction is made In this sub-section, let us see how to measure
between extensive properties and intensive heat transferred to a system. This heat
properties. An extensive property is a appears as a rise in temperature of the system
property whose value depends on the quantity in case of heat absorbed by the system.
or size of matter present in the system. For The increase of temperature is proportional
example, mass, volume, internal energy, to the heat transferred
enthalpy, heat capacity, etc. are extensive
q  coeff  T
properties.
The magnitude of the coefficient depends
Those properties which do not depend on the size, composition and nature of the
on the quantity or size of matter present system. We can also write it as q = C ∆T
are known as intensive properties. For
example temperature, density, pressure etc. The coefficient, C is called the heat
are intensive properties. A molar property, capacity.
χm, is the value of an extensive property χ of Thus, we can measure the heat supplied
the system for 1 mol of the substance. If n is by monitoring the temperature rise, provided
 we know the heat capacity.
the amount of matter,  m  n is independent When C is large, a given amount of heat
of the amount of matter. Other examples are results in only a small temperature rise. Water
molar volume, Vm and molar heat capacity, has a large heat capacity i.e., a lot of energy
C m . Let us understand the distinction is needed to raise its temperature.
between extensive and intensive properties by
C is directly proportional to amount of
considering a gas enclosed in a container of
substance. The molar heat capacity of a
volume V and at temperature T [Fig. 5.6(a)].
Let us make a partition such that volume substance, Cm =  C  , is the heat capacity
is halved, each part [Fig. 5.6 (b)] now has n
for one mole of the substance and is
one half of the original volume, V , but the
2 the quantity of heat needed to raise the
temperature will still remain the same i.e., T. temperature of one mole by one degree
It is clear that volume is an extensive property celsius (or one kelvin). Specific heat, also
and temperature is an intensive property. called specific heat capacity is the quantity

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 THERMODYNAMICS 145

of heat required to raise the temperature of i) at constant volume, qV

one unit mass of a substance by one degree ii) at constant pressure, qp
celsius (or one kelvin). For finding out the
heat, q, required to raise the temperatures (a) ∆U Measurements
of a sample, we multiply the specific heat For chemical reactions, heat absorbed at
of the substance, c, by the mass m, and constant volume, is measured in a bomb
temperatures change, ∆T as calorimeter (Fig. 5.7). Here, a steel vessel (the
q  c  m  T  C T (5.11) bomb) is immersed in a water bath. The whole
device is called calorimeter. The steel vessel is
(d) The Relationship between Cp and CV
immersed in water bath to ensure that no heat
for an Ideal Gas
is lost to the surroundings. A combustible
At constant volume, the heat capacity, C is
denoted by CV and at constant pressure, this
is denoted by Cp . Let us find the relationship
between the two.
We can write equation for heat, q
at constant volume as qV = CV T  U
at constant pressure as qp = C p T  H
The difference between Cp and CV can be
derived for an ideal gas as:
For a mole of an ideal gas, ∆H = ∆U + ∆(pV )
= ∆U + ∆(RT )
   = ∆U + R∆T
 H  U  R T (5.12)
On putting the values of ∆H and ∆U,
we have
C p T  CV T  RT
C p  CV  R Fig. 5.7 Bomb calorimeter

Cp – CV = R (5.13) substance is burnt in pure dioxygen supplied

in the steel bomb. Heat evolved during the
5.3 Measurement of ∆U and ∆H:
reaction is transferred to the water around the
Calorimetry
bomb and its temperature is monitored. Since
We can measure energy changes associated the bomb calorimeter is sealed, its volume
with chemical or physical processes by an does not change i.e., the energy changes
experimental technique called calorimetry. associated with reactions are measured at
In calorimetry, the process is carried out in a constant volume. Under these conditions, no
vessel called calorimeter, which is immersed work is done as the reaction is carried out
in a known volume of a liquid. Knowing at constant volume in the bomb calorimeter.
the heat capacity of the liquid in which Even for reactions involving gases, there is no
calorimeter is immersed and the heat capacity work done as ∆V = 0. Temperature change of
of calorimeter, it is possible to determine the the calorimeter produced by the completed
heat evolved in the process by measuring reaction is then converted to qV, by using the
temperature changes. Measurements are known heat capacity of the calorimeter with
made under two different conditions: the help of equation 5.11.

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 146 chemIstry

(b) ∆H Measurements of the bomb calorimeter is 20.7kJ/K,

Measurement of heat change at constant what is the enthalpy change for the above
pressure (generally under atmospheric pressure) reaction at 298 K and 1 atm?
can be done in a calorimeter shown in Fig. 5.8.
We know that ∆Η = qp (at constant p) and, Solution
therefore, heat absorbed or evolved, qp at Suppose q is the quantity of heat from
constant pressure is also called the heat of the reaction mixture and C V is the
reaction or enthalpy of reaction, ∆rH. heat capacity of the calorimeter, then
the quantity of heat absorbed by the
In an exothermic reaction, heat is evolved, calorimeter.
and system loses heat to the surroundings.
Therefore, qp will be negative and ∆rH will q = CV × ∆T
also be negative. Similarly in an endothermic Quantity of heat from the reaction will
reaction, heat is absorbed, qp is positive and have the same magnitude but opposite
∆rH will be positive. sign because the heat lost by the system
(reaction mixture) is equal to the heat
gained by the calorimeter.
q = –CV × ∆T = – 20.7 kJ/K × (299 – 298) K
= – 20.7 kJ
(Here, negative sign indicates the
exothermic nature of the reaction)
Thus, ∆U for the combustion of the 1g of
graphite = – 20.7 kJK–1
For combustion of 1 mol of graphite,
12.0 g mol 1   20.7 kJ 
=
1g
= – 2.48 ×102 kJ mol–1 ,  Since ∆ ng = 0,
∆ H = ∆ U = – 2.48 ×102 kJ mol–1

5.4 Enthalpy change, ∆ r H of a

reaction – Reaction Enthalpy
In a chemical reaction, reactants are converted
Fig. 5.8 Calorimeter for measuring heat changes into products and is represented by,
at constant pressure (atmospheric
Reactants → Products
pressure).
The enthalpy change accompanying a
reaction is called the reaction enthalpy. The
Problem 5.6 enthalpy change of a chemical reaction, is
1g of graphite is burnt in a bomb given by the symbol ∆rH
calorimeter in excess of oxygen at 298 K ∆rH = (sum of enthalpies of products) – (sum
and 1 atmospheric pressure according of enthalpies of reactants)
to the equation
C (graphite) + O (g) → CO (g)
 a H i products   bi H reactants (5.14)
2 2 i i

During the reaction, temperature rises

from 298 K to 299 K. If the heat capacity
Here symbol ∑ (sigma) is used for
summation and ai and bi are the stoichiometric

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 THERMODYNAMICS 147

coefficients of the products and reactants ethanol at 298 K is pure liquid ethanol at
respectively in the balanced chemical 1 bar; standard state of solid iron at 500 K
equation. For example, for the reaction is pure iron at 1 bar. Usually data are taken
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) at 298 K.
=∆r H ∑ a i H Pr oducts − ∑ bi H reac tan ts Standard conditions are denoted by
i i adding the superscript  to the symbol ∆H,
= [Hm (CO2, g) + 2Hm (H2O, l)]– [Hm (CH4, g)
e.g., ∆H
+ 2Hm (O2, g)]
where Hm is the molar enthalpy. (b) Enthalpy Changes during Phase
Transformations
Enthalpy change is a very useful quantity.
Knowledge of this quantity is required when Phase transformations also involve energy
one needs to plan the heating or cooling changes. Ice, for example, requires heat for
required to maintain an industrial chemical melting. Normally this melting takes place at
reaction at constant temperature. It is also constant pressure (atmospheric pressure) and
required to calculate temperature dependence during phase change, temperature remains
of equilibrium constant. constant (at 273 K).
(a) Standard Enthalpy of Reactions H2O(s) → H2O(l); ∆fusH  = 6.00 kJ moI–1
Enthalpy of a reaction depends on the Here ∆fusH is enthalpy of fusion in standard
conditions under which a reaction is carried state. If water freezes, then process is reversed
out. It is, therefore, necessary that we and equal amount of heat is given off to the
must specify some standard conditions. surroundings.
The standard enthalpy of reaction is the The enthalpy change that accompanies
enthalpy change for a reaction when all melting of one mole of a solid substance in
the participating substances are in their standard state is called standard enthalpy
standard states. of fusion or molar enthalpy of fusion,
The standard state of a substance at a ∆fusH .
specified temperature is its pure form at Melting of a solid is endothermic, so
1 bar. For example, the standard state of liquid all enthalpies of fusion are positive. Water

Table 5.1 Standard Enthalpy Changes of Fusion and Vaporisation

(Tf and Tb are melting and boiling points, respectively)

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 148 chemIstry

requires heat for evaporation. At constant

temperature of its boiling point Tb and at Solution
constant pressure: We can represent the process of
H2O(l) → H2O(g); ∆vapH = + 40.79 kJ moI–1 evaporation as
∆vapH is the standard enthalpy of vaporisation. H2 O(1) 
vaporisation
→ H2 O(g)
1mol 1mol
Amount of heat required to vaporize one
mole of a liquid at constant temperature No. of moles in 18 g H2O(l) is
and under standard pressure (1bar) is called 18g
= =1 mol
its standard enthalpy of vaporization or 18g mol –1
molar enthalpy of vaporization, ∆vapH . Heat supplied to evaporate18g water at
Sublimation is direct conversion of a 298 K = n × ∆vap H 
solid into its vapour. Solid CO2 or ‘dry ice’ = (1 mol) × (44.01 kJ mol–1)
sublimes at 195K with ∆subH=25.2 kJ mol–1; = 44.01 kJ
naphthalene sublimes slowly and for this (assuming steam behaving as an ideal
∆sub H = 73.0 kJ mol–1 . gas).
Standard enthalpy of sublimation,
∆subH is the change in enthalpy when one ∆vapU = ∆vapH – p∆V = ∆vapH – ∆ngRT
mole of a solid substance sublimes at a
constant temperature and under standard ∆vapHV – ∆ngRT = 44.01 kJ
pressure (1bar). –(1)(8.314 JK–1mol–1)(298K)(10–3kJ J–1)
The magnitude of the enthalpy change ∆vapUV = 44.01 kJ – 2.48kJ
depends on the strength of the intermolecular
= 41.53 kJ
interactions in the substance undergoing
the phase transfomations. For example,
Problem 5.8
the strong hydrogen bonds between water
molecules hold them tightly in liquid phase. Assuming the water vapour to be a perfect
gas, calculate the internal energy change
For an organic liquid, such as acetone, the
when 1 mol of water at 100°C and 1 bar
intermolecular dipole-dipole interactions are pressure is converted to ice at 0°C. Given
significantly weaker. Thus, it requires less the enthalpy of fusion of ice is 6.00 kJ
heat to vaporise 1 mol of acetone than it does mol-1 heat capacity of water is 4.2 J/g°C
to vaporize 1 mol of water. Table 5.1 gives The change take place as follows:
values of standard enthalpy changes of fusion Step - 1 1 mol H2O (l, 100°C)  1
and vaporisation for some substances. mol (l, 0°C) Enthalpy
change ∆H1
Problem 5.7
Step - 2 1 mol H2O (l, 0°C)  1 mol
A swimmer coming out from a pool is H2O( S, 0°C) Enthalpy
covered with a film of water weighing change ∆H2
about 18g. How much heat must be Total enthalpy change will be -
supplied to evaporate this water at
298 K ? Calculate the internal energy ∆H = ∆H1 + ∆H2
of vaporisation at 298K. ∆H1 = - (18 x 4.2 x 100) J mol-1
∆vap H  for water = - 7560 J mol-1 = - 7.56 k J mol-1
at 298K= 44.01kJ mol–1 ∆H2 = - 6.00 kJ mol-1

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 THERMODYNAMICS 149

Table 5.2 Standard Molar Enthalpies of Formation (∆f H ) at 298K of a Few

Selected Substances

of aggregation (also known as reference

Therefore,
states) is called Standard Molar Enthalpy
∆H = - 7.56 kJ mol-1 + (-6.00 kJ mol-1)
of Formation. Its symbol is ∆f H , where the
   = -13.56 kJ mol-1
subscript ‘ f ’ indicates that one mole of the
There is negligible change in the volume
compound in question has been formed in its
during the change form liquid to solid
state. standard state from its elements in their most
stable states of aggregation. The reference
Therefore, p∆v = ∆ng RT = 0
state of an element is its most stable state
∆H = ∆U = - 13.56kJ mol-1
of aggregation at 25°C and 1 bar pressure.
For example, the reference state of dihydrogen
(c) Standard Enthalpy of Formation is H 2 gas and those of dioxygen, carbon
The standard enthalpy change for the and sulphur are O2 gas, Cgraphite and Srhombic
formation of one mole of a compound from respectively. Some reactions with standard
its elements in their most stable states molar enthalpies of formation are as follows.

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 150 chemIstry

H2(g) + ½O2 (g) → H2O(1); Here, we can make use of standard enthalpy
of formation and calculate the enthalpy
∆f H = –285.8 kJ mol–1
change for the reaction. The following general
C (graphite, s) + 2H2(g) → Ch4 (g); equation can be used for the enthalpy change
∆f H = –74.81 kJ mol–1 calculation.
2C (graphite, s)+3H2 (g)+ ½O2(g) → C2H5OH(1); ∆rH = ∑ ai ∆f H (products) – ∑ bi ∆f H (reactants)
i
∆f H  = – 277.7kJ mol–1
i
(5.15)
It is important to understand that a where a and b represent the coefficients of
standard molar enthalpy of formation, ∆f H , the products and reactants in the balanced
is just a special case of ∆rH , where one mole equation. Let us apply the above equation for
of a compound is formed from its constituent decomposition of calcium carbonate. Here,
elements, as in the above three equations, coefficients ‘a’ and ‘b’ are 1 each. Therefore,
where 1 mol of each, water, methane and ∆rH = ∆f H  = [CaO(s)]+ ∆f H  [CO2(g)]
ethanol is formed. In contrast, the enthalpy – ∆f H  = [CaCO3(s)]
change for an exothermic reaction: =1 (–635.1 kJ mol–1) + 1(–393.5 kJ mol–1)
CaO(s) + CO2(g) → CaCo3(s);
–1(–1206.9 kJ mol–1)
∆rH  = – 178.3kJ mol–1
= 178.3 kJ mol–1
is not an enthalpy of formation of calcium
carbonate, since calcium carbonate has been Thus, the decomposition of CaCO3 (s) is
formed from other compounds, and not from an endothermic process and you have to heat
its constituent elements. Also, for the reaction it for getting the desired products.
given below, enthalpy change is not standard (d) Thermochemical Equations
enthalpy of formation, ∆fH  for HBr(g).
A balanced chemical equation together with
H2(g) + Br2(l) → 2HBr(g); the value of its ∆rH is called a thermochemical
∆r H  = – 178.3kJ mol–1 equation. We specify the physical state
Here two moles, instead of one mole of the (alongwith allotropic state) of the substance
product is formed from the elements, i.e., in an equation. For example:
∆r H  = 2∆f H C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l);
Therefore, by dividing all coefficients in ∆rH = – 1367 kJ mol–1
the balanced equation by 2, expression for The above equation describes the
enthalpy of formation of HBr (g) is written as combustion of liquid ethanol at constant
½H2(g) + ½Br2(1) → HBr(g); temperature and pressure. The negative sign
∆f H = – 36.4 kJ mol–1 of enthalpy change indicates that this is an
exothermic reaction.
Standard enthalpies of formation of some
common substances are given in Table 5.2. It would be necessary to remember the
By convention, standard enthalpy for following conventions regarding thermo-
formation, ∆f H , of an element in reference chemical equations.
state, i.e., its most stable state of aggregation 1. The coefficients in a balanced thermo-
is taken as zero. chemical equation refer to the number of
moles (never molecules) of reactants and
Suppose, you are a chemical engineer and
want to know how much heat is required to products involved in the reaction.
decompose calcium carbonate to lime and 2. The numerical value of ∆rH  refers to the
carbon dioxide, with all the substances in number of moles of substances specified
their standard state. by an equation. Standard enthalpy change
CaCO3(s) → CaO(s) + CO2(g); ∆r H = ? ∆rH will have units as kJ mol–1.

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 THERMODYNAMICS 151

To illustrate the concept, let us consider (e) Hess’s Law of Constant Heat
the calculation of heat of reaction for the Summation
following reaction : We know that enthalpy is a state function,
Fe2O3  s   3H2  g   2Fe  s   3H2O  l  , therefore the change in enthalpy is independent
of the path between initial state (reactants)
From the Table (5.2) of standard enthalpy of and final state (products). In other words,
formation (∆f H ), we find : enthalpy change for a reaction is the same
∆f H (H2O,l) = –285.83 kJ mol–1; whether it occurs in one step or in a series
∆f H (Fe2O3,s) = – 824.2 kJ mol–1; of steps. This may be stated as follows in the
form of Hess’s Law.
Also ∆f H (Fe, s) = 0 and
If a reaction takes place in several
∆f H (H2, g) = 0 as per convention
steps then its standard reaction enthalpy
Then, is the sum of the standard enthalpies of
∆f H1 = 3(–285.83 kJ mol–1) the intermediate reactions into which the
– 1(– 824.2 kJ mol–1) overall reaction may be divided at the same
temperature.
= (–857.5 + 824.2) kJ mol–1
Let us understand the importance of this
= –33.3 kJ mol–1
law with the help of an example.
Note that the coefficients used in these
Consider the enthalpy change for the
calculations are pure numbers, which
reaction
are equal to the respective stoichiometric
c o e f f i c i e n t s . T h e u n i t f o r ∆ rH  i s C (graphite,s) + O2 (g) → CO (g); ∆r H  = ?
kJ mol–1, which means per mole of reaction. Although CO(g) is the major product, some
Once we balance the chemical equation in a CO2 gas is always produced in this reaction.
particular way, as above, this defines the mole Therefore, we cannot measure enthalpy
of reaction. If we had balanced the equation change for the above reaction directly.
differently, for example, However, if we can find some other reactions
1 3 3 involving related species, it is possible to
Fe2O3  s   H2  g   Fe  s   H2O  l 
2 2 2 calculate the enthalpy change for the above
reaction.
then this amount of reaction would be one
mole of reaction and ∆rH  would be Let us consider the following reactions:
3 C (graphite,s) + O2 (g) → CO2 (g);
∆f H 
2
= (–285.83 kJ mol–1)
2 ∆r H  = – 393.5 kJ mol–1 (i)
1
– (–824.2 kJ mol–1) 1
2 CO (g) + O (g) → CO2 (g)
= (– 428.7 + 412.1) kJ mol–1 2 2 ∆r H  = – 283.0 kJ mol–1 (ii)
= –16.6 kJ mol–1 = ½ ∆r H 1 We can combine the above two reactions
It shows that enthalpy is an extensive in such a way so as to obtain the desired
quantity. reaction. To get one mole of CO(g) on the
3. When a chemical equation is reversed, right, we reverse equation (ii). In this, heat
the value of ∆rH  is reversed in sign. For is absorbed instead of being released, so we
example change sign of ∆rH  value
N2(g) + 3H2 (g) → 2NH3 (g); CO2 (g) → CO (g) + O2 (g);
∆r H  = – 91.8 kJ. mol–1 ∆r H  = + 283.0 kJ mol–1 (iii)
2NH3(g) → N2(g) + 3H2 (g);
∆r H  = + 91.8 kJ mol–1

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 152 chemIstry

Adding equation (i) and (iii), we get the Similarly, combustion of glucose gives out
desired equation, 2802.0 kJ/mol of heat, for which the overall
1 equation is :
C  graphite, s   O2  g   CO  g  ;
2 C6 H12O6 ( g )  6O2 ( g )  6CO2 ( g )  6H2O(1);
for which ∆r H  = (– 393.5 + 283.0) ∆C H  = – 2802.0 kJ mol–1
= – 110.5 kJ mol–1 Our body also generates energy from food
by the same overall process as combustion,
In general, if enthalpy of an overall although the final products are produced after
reaction A→B along one route is ∆rH and a series of complex bio-chemical reactions
∆rH1, ∆rH2, ∆rH3..... representing enthalpies involving enzymes.
of reactions leading to same product, B along
another route, then we have
Problem 5.9
∆rH = ∆rH1 + ∆rH2 + ∆rH3 ... (5.16)
The combustion of one mole of benzene
It can be represented as:
takes place at 298 K and 1 atm. After
combustion, CO2(g) and H2O (1) are
∆rH produced and 3267.0 kJ of heat is
A B
liberated. Calculate the standard
∆H1 ∆rH3 enthalpy of formation, ∆f H  of benzene.
Standard enthalpies of formation of
C D CO2(g) and H2O(l) are –393.5 kJ mol–1
∆rH2 and – 285.83 kJ mol–1 respectively.

5.5 Enthalpies for different types Solution

of reactions The formation reaction of benezene is
It is convenient to give name to enthalpies given by :
specifying the types of reactions. 6C  graphite   3H2  g   C6 H6  l  ;
(a) Standard Enthalpy of Combustion ∆f H  = ? ... (i)
(symbol : ∆cH )
The enthalpy of combustion of 1 mol
Combustion reactions are exothermic in of benzene is :
nature. These are important in industry, 15
rocketry, and other walks of life. Standard C6 H6  l   O2  6CO2  g   3H2O  l  ;
enthalpy of combustion is defined as the 2
enthalpy change per mole (or per unit amount) ∆C H  = – 3267 kJ mol–1... (ii)
of a substance, when it undergoes combustion The enthalpy of formation of 1 mol of
and all the reactants and products being CO2(g) :
in their standard states at the specified C  graphite   O2  g   CO2  g  ;
temperature.
∆f H  = – 393.5 kJ mol–1... (iii)
Cooking gas in cylinders contains mostly
butane (C4H10). During complete combustion The enthalpy of formation of 1 mol of
of one mole of butane, 2658 kJ of heat is H2O(l) is :
released. We can write the thermochemical 1
H2  g   O2  g   H2 O  l  ;
reactions for this as: 2
13 ∆C H  = – 285.83 kJ mol–1... (iv)
C4 H10 ( g )  O2 ( g )  4CO2 ( g )  5H2O(1);
2 multiplying eqn. (iii) by 6 and eqn. (iv)
∆C H  = – 2658.0 kJ mol–1 by 3 we get:

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 THERMODYNAMICS 153

In this case, the enthalpy of atomization is

6C  graphite   6O2  g   6CO2  g  ; same as the enthalpy of sublimation.

∆f H  = – 2361 kJ mol–1 (c) Bond Enthalpy (symbol: ∆bondH )

3 Chemical reactions involve the breaking and
3H 2  g   O2  g   3H2O 1 ; making of chemical bonds. Energy is required
2
to break a bond and energy is released when a
∆f H  = – 857.49 kJ mol–1
bond is formed. It is possible to relate heat of
Summing up the above two equations : reaction to changes in energy associated with
15 breaking and making of chemical bonds. With
6C  graphite   3H2  g   O2  g   6CO2  g 
2 reference to the enthalpy changes associated
 3H 2 O  l  ; with chemical bonds, two different terms are
used in thermodynamics.
∆f H  = – 3218.49 kJ mol–1... (v)
(i) Bond dissociation enthalpy
Reversing equation (ii);
(ii) Mean bond enthalpy
15
6CO2  g   3H2O  l   C6 H6  l   O2 ; Let us discuss these terms with reference
2
to diatomic and polyatomic molecules.
∆f H  = – 3267.0 kJ mol–1... (vi) Diatomic Molecules: Consider the following
Adding equations (v) and (vi), we get process in which the bonds in one mole of
6C  graphite   3H2  g   C6 H6  l  ; dihydrogen gas (H2) are broken:
H2(g) → 2H(g); ∆H–HH  = 435.0 kJ mol–1
∆f H  = – 48.51 kJ mol–1... (iv) The enthalpy change involved in this process
is the bond dissociation enthalpy of H–H
bond. The bond dissociation enthalpy is the
(b) Enthalpy of Atomization change in enthalpy when one mole of covalent
(symbol: ∆aH ) bonds of a gaseous covalent compound is
Consider the following example of atomization broken to form products in the gas phase.
of dihydrogen Note that it is the same as the enthalpy of
H2(g) → 2H(g); ∆aH  = 435.0 kJ mol–1 atomization of dihydrogen. This is true for all
You can see that H atoms are formed by diatomic molecules. For example:
breaking H–H bonds in dihydrogen. The Cl2(g) → 2Cl(g); ∆Cl–ClH  = 242 kJ mol–1
enthalpy change in this process is known
as enthalpy of atomization, ∆aH . It is the O2(g) → 2O(g); ∆O=OH = 428 kJ mol–1
enthalpy change on breaking one mole of In the case of polyatomic molecules, bond
bonds completely to obtain atoms in the gas dissociation enthalpy is different for different
phase. bonds within the same molecule.
In case of diatomic molecules, like Polyatomic Molecules: Let us now consider
dihydrogen (given above), the enthalpy of a polyatomic molecule like methane, CH4.
atomization is also the bond dissociation The overall thermochemical equation for its
enthalpy. The other examples of enthalpy of atomization reaction is given below:
atomization can be CH4 (g) → C(g) + 4H(g);
CH4(g) → C(g) + 4H(g); ∆aH = 1665 kJ mol
 –1
∆a H  = 1665 kJ mol–1
Note that the products are only atoms of C In methane, all the four C – H bonds are
and H in gaseous phase. Now see the following identical in bond length and energy. However,
reaction: the energies required to break the individual
Na(s) → Na(g); ∆aH = 108.4 kJ mol–1 C – H bonds in each successive step differ :

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 154 chemIstry

CH4(g) → CH3(g)+H(g);∆bond H = +427 kJ mol–1 given in Table 5.3. The reaction enthalpies are
CH3(g) → CH2(g)+H(g);∆bond H = +439 kJ mol
 –1 very important quantities as these arise from
the changes that accompany the breaking of
CH2(g) → CH(g)+H(g);∆bond H = +452 kJ mol–1 old bonds and formation of the new bonds.
CH(g) → C(g)+H(g);∆bond H = +347 kJ mol–1 We can predict enthalpy of a reaction in gas
Therefore, phase, if we know different bond enthalpies.
The standard enthalpy of reaction, ∆rH is
CH4(g) → C(g)+4H(g);∆a H = 1665 kJ mol–1 related to bond enthalpies of the reactants
In such cases we use mean bond enthalpy and products in gas phase reactions as:
of C – H bond.
For example in CH4, ∆C–HH  is calculated as: ∆r H   bond enthalpiesreactants
∆C–HH = ¼ (∆a H) = ¼ (1665 kJ mol–1)   bond enthalpies products
(5.17)**
= 416 kJ mol–1 This relationship is particularly more
We find that mean C–H bond enthalpy useful when the required values of ∆f H are
in methane is 416 kJ/mol. It has been not available. The net enthalpy change of a
found that mean C–H bond enthalpies differ reaction is the amount of energy required
slightly from compound to compound, as to break all the bonds in the reactant
in CH3CH2Cl, CH3NO2, etc., but it does not molecules minus the amount of energy
differ in a great deal*. Using Hess’s law, bond required to break all the bonds in the product
enthalpies can be calculated. Bond enthalpy molecules. Remember that this relationship is
values of some single and multiple bonds are approximate and is valid when all substances

Table 5.3(a) Some Mean Single Bond Enthalpies in kJ mol–1 at 298 K

H C N O F Si P S Cl Br I
435.8 414 389 464 569 293 318 339 431 368 297 H
347 293 351 439 289 264 259 330 276 238 C
159 201 272 - 209 - 201 243 - N
138 184 368 351 - 205 - 201 O
155 540 490 327 255 197 - F
176 213 226 360 289 213 Si
213 230 331 272 213 P
213 251 213 - S
243 218 209 CI
192 180 Br
151 I

Table 5.3(b) Some Mean Multiple Bond Enthalpies in kJ mol–1 at 298 K

N=N 418 C = C 611 O = O 498

N≡N 946 C ≡ C 837
C=N 615 C = O 741
C≡N 891 C ≡ O 1070

* Note that symbol used for bond dissociation enthalpy and mean bond enthalpy is the same.
** If we use enthalpy of bond formation, (∆f Hbond), which is the enthalpy change when one mole of a particular type of
bond is formed from gaseous atom, then ∆f H  = ∑ ∆f Hbonds of products – ∑ ∆f H bonds of reactants

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 THERMODYNAMICS 155

(reactants and products) in the reaction are  1

2. Na( g )  Na ( g )  e ( g ) , the ionization of
in gaseous state.
sodium atoms, ionization enthalpy
(d) Lattice Enthalpy ∆iH = 496 kJ mol–1

The lattice enthalpy of an ionic compound is 3. 1 Cl 2 ( g ) → Cl( g ), t h e d i s s o c i a t i o n o f

the enthalpy change which occurs when one 2
mole of an ionic compound dissociates into chlorine, the reaction enthalpy is half the
its ions in gaseous state. bond dissociation enthalpy.
Na  Cl   s   Na  ( g )  Cl   g  ; 1 ∆ H = 121 kJ mol–1
bond
2
∆latticeH  = +788 kJ mol–1
Since it is impossible to determine lattice 4. Cl( g )  e 1 ( g )  Cl( g ) e l e c t r o n g a i n e d
enthalpies directly by experiment, we use by chlorine atoms. The electron gain
enthalpy, ∆egH  = – 348.6 kJ mol–1.
an indirect method where we construct an
You have learnt about ionization enthalpy
enthalpy diagram called a Born-Haber Cycle
and electron gain enthalpy in Unit 3.
(Fig. 5.9).
In fact, these terms have been taken
Let us now calculate the lattice enthalpy from thermodynamics. Earlier terms,
of Na+Cl–(s) by following steps given below : ionization energy and electron affinity
1. Na( s ) → Na( g ) , sublimation of sodium were in practice in place of the above
metal, ∆subH  = 108.4 kJ mol–1 terms (see the box for justification).

Ionization Energy and Electron Affinity

Ionization energy and electron affinity
are defined at absolute zero. At any other
temperature, heat capacities for the reactants
and the products have to be taken into
account. Enthalpies of reactions for
M(g) → M+(g) + e– (for ionization)
M(g) + e –
→ M (g) (for electron gain)
–

at temperature, T is
T
∆rH (T ) = ∆rH(0) + ∫
0
∆rCPdT

The value of Cp for each species in the above

reaction is 5/2 R (CV = 3/2R)
So, ∆rCp = + 5/2 R (for ionization)
∆rCp = – 5/2 R (for electron gain)
Therefore,
∆rH  (ionization enthalpy)
= E0 (ionization energy) + 5/2 RT
∆rH (electron gain enthalpy)
= – A( electron affinity) – 5/2 RT

5. Na + (g) + Cl − (g) → Na + Cl − (s)

Fig. 5.9 Enthalpy diagram for lattice enthalpy of The sequence of steps is shown in
NaCl Fig. 5.9, and is known as a Born-Haber

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 156 chemIstry

cycle. The importance of the cycle is that, The enthalpy of solution of AB(s), ∆solH ,
the sum of the enthalpy changes round a in water is, therefore, determined by the
cycle is zero. Applying Hess’s law, we get, selective values of the lattice enthalpy, ∆latticeH
∆latticeH = 411.2 + 108.4 + 121 + 496 – 348.6 and enthalpy of hydration of ions, ∆hydH as
∆sol H  = ∆latticeH  + ∆hydH 
∆latticeH = + 788kJ
for NaCl(s)  Na+(g) + Cl–(g) For most of the ionic compounds, ∆sol
Internal energy is smaller by 2RT (because ∆ng H is positive and the dissociation process
= 2) and is equal to + 783 kJ mol–1. is endothermic. Therefore the solubility of
most salts in water increases with rise of
Now we use the value of lattice enthalpy temperature. If the lattice enthalpy is very
to calculate enthalpy of solution from the high, the dissolution of the compound may
expression: not take place at all. Why do many fluorides
∆solH = ∆latticeH + ∆hydH tend to be less soluble than the corresponding
For one mole of NaCl(s), chlorides? Estimates of the magnitudes of
lattice enthalpy = + 788 kJ mol–1 enthalpy changes may be made by using
and ∆hydH  = – 784 kJ mol–1( from the tables of bond energies (enthalpies) and lattice
literature) energies (enthalpies).
∆sol H = + 788 kJ mol–1 – 784 kJ mol–1 (f) Enthalpy of Dilution
= + 4 kJ mol–1 It is known that enthalpy of solution is the
The dissolution of NaCl(s) is accompanied enthalpy change associated with the addition
by very little heat change. of a specified amount of solute to the specified
(e) Enthalpy of Solution (symbol : ∆solH ) amount of solvent at a constant temperature
and pressure. This argument can be applied
Enthalpy of solution of a substance is the
to any solvent with slight modification.
enthalpy change when one mole of it dissolves
Enthalpy change for dissolving one mole of
in a specified amount of solvent. The enthalpy
gaseous hydrogen chloride in 10 mol of water
of solution at infinite dilution is the enthalpy
can be represented by the following equation.
change observed on dissolving the substance
For convenience we will use the symbol aq.
in an infinite amount of solvent when the
interactions between the ions (or solute for water
molecules) are negligible. HCl(g) + 10 aq. → HCl.10 aq.
When an ionic compound dissolves in a ∆H = –69.01 kJ / mol
solvent, the ions leave their ordered positions Let us consider the following set of
on the crystal lattice. These are now more free in enthalpy changes:
solution. But solvation of these ions (hydration
(S-1) HCl(g) + 25 aq. → HCl.25 aq.
in case solvent is water) also occurs at the
∆H = –72.03 kJ / mol
same time. This is shown diagrammatically,
for an ionic compound, AB (s) (S-2) HCl(g) + 40 aq. → HCl.40 aq.
∆H = –72.79 kJ / mol
(S-3) HCl(g) + ∞ aq. → HCl. ∞ aq.
∆H = –74.85 kJ / mol
The values of ∆H show general dependence
of the enthalpy of solution on amount of
solvent. As more and more solvent is used,
the enthalpy of solution approaches a limiting
value, i.e, the value in infinitely dilute
solution. For hydrochloric acid this value of
∆H is given above in equation (S-3).

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 THERMODYNAMICS 157

If we subtract the first equation (equation many years without observing any perceptible
S-1) from the second equation (equation S-2) change. Although the reaction is taking place
in the above set of equations, we obtain– between them, it is at an extremely slow
rate. It is still called spontaneous reaction.
HCl.25 aq. + 15 aq. → HCl.40 aq.
So spontaneity means ‘having the potential
∆H = [ –72.79 – (–72.03)] kJ / mol to proceed without the assistance of external
= – 0.76 kJ / mol agency’. However, it does not tell about the
This value (–0.76kJ/mol) of ∆H is enthalpy rate of the reaction or process. Another aspect
of dilution. It is the heat withdrawn from of spontaneous reaction or process, as we see
the surroundings when additional solvent is is that these cannot reverse their direction on
added to the solution. The enthalpy of dilution their own. We may summarise it as follows:
of a solution is dependent on the original A spontaneous process is an
concentration of the solution and the amount irreversible process and may only be
of solvent added. reversed by some external agency.
5.6 spontaneity (a) Is Decrease in Enthalpy a Criterion
The first law of thermodynamics tells us for Spontaneity ?
about the relationship between the heat If we examine the phenomenon like flow of
absorbed and the work performed on or water down hill or fall of a stone on to the
by a system. It puts no restrictions on ground, we find that there is a net decrease
the direction of heat flow. However, the in potential energy in the direction of change.
flow of heat is unidirectional from higher By analogy, we may be tempted to state that
temperature to lower temperature. In fact, a chemical reaction is spontaneous in a
all naturally occurring processes whether given direction, because decrease in energy
chemical or physical will tend to proceed has taken place, as in the case of exothermic
spontaneously in one direction only. For reactions. For example:
example, a gas expanding to fill the available 1
volume, burning carbon in dioxygen giving N (g) + H2(g) = NH3(g);
2 2
carbon dioxide. ∆r H  = – 46.1 kJ mol–1
But heat will not flow from colder body to 1 1
warmer body on its own, the gas in a container H (g) + Cl2(g) = HCl (g);
2 2 2
will not spontaneously contract into one ∆r H  = – 92.32 kJ mol–1
corner or carbon dioxide will not form carbon 1
H2(g) + O2(g) → H2O(l) ;
and dioxygen spontaneously. These and many 2 ∆ H  = –285.8 kJ mol–1
other spontaneously occurring changes show r

unidirectional change. We may ask ‘what is The decrease in enthalpy in passing from
the driving force of spontaneously occurring reactants to products may be shown for any
changes ? What determines the direction of a exothermic reaction on an enthalpy diagram
spontaneous change ? In this section, we shall as shown in Fig. 5.10(a).
establish some criterion for these processes Thus, the postulate that driving force for
whether these will take place or not. a chemical reaction may be due to decrease
Let us first understand what do we mean in energy sounds ‘reasonable’ as the basis of
by spontaneous reaction or change ? You evidence so far !
may think by your common observation that Now let us examine the following reactions:
spontaneous reaction is one which occurs 1
N2(g) + O2(g) → NO2(g);
immediately when contact is made between 2
the reactants. Take the case of combination ∆r H = +33.2 kJ mol–1
of hydrogen and oxygen. These gases may C(graphite, s) + 2 S(l) → CS2(l);
be mixed at room temperature and left for ∆r H = +128.5 kJ mol–1

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 158 chemIstry

Fig. 5.10 (a) Enthalpy diagram for exothermic

reactions
These reactions though endothermic, are
spontaneous. The increase in enthalpy may
be represented on an enthalpy diagram as
shown in Fig. 5.10(b).

Fig. 5.11 Diffusion of two gases

respectively and separated by a movable

partition [Fig. 5.11 (a)]. When the partition is
withdrawn [Fig. 5.11(b)], the gases begin to
diffuse into each other and after a period of
time, diffusion will be complete.
Let us examine the process. Before
partition, if we were to pick up the gas
molecules from left container, we would be
Fig. 5.10 (b) Enthalpy diagram for endothermic sure that these will be molecules of gas A
reactions and similarly if we were to pick up the gas
molecules from right container, we would
Therefore, it becomes obvious that while
be sure that these will be molecules of gas
decrease in enthalpy may be a contributory
B. But, if we were to pick up molecules from
factor for spontaneity, but it is not true for
container when partition is removed, we are
all cases.
not sure whether the molecules picked are of
(b) Entropy and Spontaneity gas A or gas B. We say that the system has
Then, what drives the spontaneous process become less predictable or more chaotic.
in a given direction ? Let us examine such a We may now formulate another postulate:
case in which ∆H = 0 i.e., there is no change in in an isolated system, there is always a
enthalpy, but still the process is spontaneous. tendency for the systems’ energy to become
Let us consider diffusion of two gases more disordered or chaotic and this could be
into each other in a closed container which a criterion for spontaneous change !
is isolated from the surroundings as shown At this point, we introduce another
in Fig. 5.11. thermodynamic function, entropy denoted
The two gases, say, gas A and gas B are as S. The above mentioned disorder is the
represented by black dots and white dots manifestation of entropy. To form a mental

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 THERMODYNAMICS 159

picture, one can think of entropy as a measure qrev

of the degree of randomness or disorder in the ∆S = (5.18)
T
system. The greater the disorder in an isolated The total entropy change (∆Stotal) for the
system, the higher is the entropy. As far as a system and surroundings of a spontaneous
chemical reaction is concerned, this entropy process is given by
change can be attributed to rearrangement of
Stotal  Ssystem  Ssurr  0 (5.19)
atoms or ions from one pattern in the reactants
to another (in the products). If the structure When a system is in equilibrium, the
of the products is very much disordered than entropy is maximum, and the change in
that of the reactants, there will be a resultant entropy, ∆S = 0.
increase in entropy. The change in entropy
We can say that entropy for a spontaneous
accompanying a chemical reaction may be
process increases till it reaches maximum
estimated qualitatively by a consideration of
and at equilibrium the change in entropy is
the structures of the species taking part in the
zero. Since entropy is a state property, we can
reaction. Decrease of regularity in structure
calculate the change in entropy of a reversible
would mean increase in entropy. For a given
process by
substance, the crystalline solid state is the
state of lowest entropy (most ordered), The qsys ,rev
gaseous state is state of highest entropy. ∆Ssys =
T
Now let us try to quantify entropy. One way We find that both for reversible and
to calculate the degree of disorder or chaotic irreversible expansion for an ideal gas, under
distribution of energy among molecules isothermal conditions, ∆U = 0,  but ∆S total
would be through statistical method which
i.e., Ssys  Ssurr is not zero for irreversible
is beyond the scope of this treatment. Other
process. Thus,  ∆U does not discriminate
way would be to relate this process to the
between reversible and irreversible process,
heat involved in a process which would make
whereas ∆S does.
entropy a thermodynamic concept. Entropy,
like any other thermodynamic property such
as internal energy U and enthalpy H is a state Problem 5.10
function and ∆S is independent of path.
Predict in which of the following, entropy
Whenever heat is added to the system, increases/decreases :
it increases molecular motions causing (i) A liquid crystallizes into a solid.
increased randomness in the system. Thus
(ii) Temperature of a crystalline solid
heat (q) has randomising influence on the
is raised from 0 K to 115 K.
system. Can we then equate ∆S with q ? Wait !
Experience suggests us that the distribution  iii  2NaHCO3  s   Na 2 CO3  s  
of heat also depends on the temperature at CO2  g   H2O  g 
which heat is added to the system. A system at
higher temperature has greater randomness (iv) H2  g   2H  g 
in it  than one at lower temperature. Thus,
Solution
temperature is the measure of average
chaotic motion of particles in the system. (i) After freezing, the molecules attain
Heat added to a system at lower temperature an ordered state and therefore,
causes greater randomness than when the entropy decreases.
same quantity of heat is added to it at higher (ii) At 0 K, the contituent particles are
temperature. This suggests that the entropy static and entropy is minimum.
change is inversely proportional to the If temperature is raised to 115 K,
temperature. ∆S is related with q and T for a these begin to move and oscillate
reversible reaction as :

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 160 chemIstry

about their equilibrium positions = 4980.6 JK–1 mol–1

in the lattice and system becomes This shows that the above reaction is
more disordered, therefore entropy spontaneous.
increases.
(iii) Reactant, NaHCO3 is a solid and it (c) Gibbs Energy and Spontaneity
has low entropy. Among products We have seen that for a system, it is the
there are one solid and two gases. total entropy change, ∆Stotal which decides
Therefore, the products represent a the spontaneity of the process. But most of
condition of higher entropy. the chemical reactions fall into the category
(iv) Here one molecule gives two atoms of either closed systems or open systems.
i.e., number of particles increases Therefore, for most of the chemical reactions
leading to more disordered state. there are changes in both enthalpy and
Two moles of H atoms have entropy. It is clear from the discussion in
higher entropy than one mole of previous sections that neither decrease in
dihydrogen molecule. enthalpy nor increase in entropy alone can
Problem 5.11 determine the direction of spontaneous
change for these systems.
For oxidation of iron,
For this purpose, we define a new
4Fe  s   3O2  g   2Fe2O3  s  thermodynamic function the Gibbs energy
entropy change is – 549.4 JK–1 mol–1 or Gibbs function, G, as
at 298 K. Inspite of negative entropy G = H – TS (5.20)
change of this reaction, why is the Gibbs function, G is an extensive property
reaction spontaneous? and a state function.
(∆rH  for this reaction is The change in Gibbs energy for the
–1648 × 103 J mol–1) system, ∆Gsys can be written as
Solution Gsys = H sys  T Ssys  Ssys T
One decides the spontaneity of a
reaction by considering At constant temperature,

 
Stotal Ssys  Ssurr . For calculating  Gsys = H sys  T Ssys
∆Ssurr, we have to consider the heat Usually the subscript ‘system’ is dropped
absorbed by the surroundings which
and we simply write this equation as
is equal to – ∆rH . At temperature T,
entropy change of the surroundings is G  H  T S (5.21)
Thus, Gibbs energy change = enthalpy
change – temperature × entropy change, and
is referred to as the Gibbs equation, one of

 1648 10 3
J mol 1  the most important equations in chemistry.
298 K Here, we have considered both terms together
for spontaneity: energy (in terms of ∆H)
= 5530 JK–1mol–1 and entropy (∆S, a measure of disorder) as
Thus, total entropy change for this indicated earlier. Dimensionally if we analyse,
reaction we find that ∆G has units of energy because,
r Stotal  5530 JK –1mol –1  both ∆H and the T∆S are energy terms, since
 549.4 JK –1
mol –1  T∆S = (K) (J/K) = J.
Now let us consider how ∆G is related to
reaction spontaneity.

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 THERMODYNAMICS 161

We know, be small. The former is one of the reasons

∆Stotal = ∆Ssys + ∆Ssurr why reactions are often carried out at high
If the system is in thermal equilibrium with temperature. Table 5.4 summarises the effect
the surrounding, then the temperature of the of temperature on spontaneity of reactions.
surrounding is same as that of the system. (d) Entropy and Second Law of
Also, increase in enthalpy of the surrounding Thermodynamics
is equal to decrease in the enthalpy of the
We know that for an isolated system
system.
the change in energy remains constant.
Therefore, entropy change of surroundings, Therefore, increase in entropy in such
H surr H sys systems is the natural direction of a
Ssurr =  spontaneous change. This, in fact is the
T T
second law of thermodynamics. Like first
 H sys  law of thermodynamics, second law can also
Stotal  Ssys   
 T  be stated in several ways. The second law of
thermodynamics explains why spontaneous
Rearranging the above equation:
exothermic reactions are so common.
T∆Stotal = T∆Ssys – ∆Hsys In exothermic reactions heat released
For spontaneous process, Stotal  0 , so by the reaction increases the disorder
T∆Ssys – ∆Hsys > Ο of the surroundings and overall entropy
change is positive which makes the reaction
 
  H sys  T Ssys  0 spontaneous.

Using equation 5.21, the above equation can (e) Absolute Entropy and Third Law of
be written as Thermodynamics
–∆G > O Molecules of a substance may move in a
G  H  T S  0 straight line in any direction, they may
(5.22) spin like a top and the bonds in the
∆Hsys is the enthalpy change of a reaction, molecules may stretch and compress.
T∆Ssys is the energy which is not available to do These motions of the molecule are called
useful work. So ∆G is the net energy available translational, rotational and vibrational
to do useful work and is thus a measure of the motion respectively. When temperature of
‘free energy’. For this reason, it is also known the system rises, these motions become
as the free energy of the reaction. more vigorous and entropy increases. On the
∆G gives a criteria for spontaneity at other hand when temperature is lowered, the
constant pressure and temperature. entropy decreases. The entropy of any pure
crystalline substance approaches zero as
(i) If ∆G is negative (< 0), the process is the temperature approaches absolute zero.
spontaneous. This is called third law of thermodynamics.
(ii) If ∆G is positive (> 0), the process is non This is so because there is perfect order in
spontaneous. a crystal at absolute zero. The statement is
confined to pure crystalline solids because
Note : If a reaction has a positive enthalpy
theoretical arguments and practical evidences
change and positive entropy change, it can
have shown that entropy of solutions and
be spontaneous when T∆S is large enough to
super cooled liquids is not zero at 0 K. The
outweigh ∆H. This can happen in two ways; importance of the third law lies in the fact that
(a) The positive entropy change of the system it permits the calculation of absolute values
can be ‘small’ in which case T must be of entropy of pure substance from thermal
large. (b) The positive entropy change of the data alone. For a pure substance, this can
system can be ‘large’, in which case T may

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 162 chemIstry

n
q is minimum. If it is not, the system would
be done by summing rev increments from 0
T spontaneously change to configuration of
K to 298 K. Standard entropies can be used lower free energy.
to calculate standard entropy changes by a So, the criterion for equilibrium
Hess’s law type of calculation. A + B  C + D; is
∆rG = 0
5.7 G i bb s e n e r g y c h a n g e a n d
Gibbs energy for a reaction in which all
equilibrium
reactants and products are in standard state,
We have seen how a knowledge of the sign ∆rG  is related to the equilibrium constant of
and magnitude of the free energy change of a the reaction as follows:
chemical reaction allows: 0 = ∆rG  + RT ln K
(i) Prediction of the spontaneity of the or ∆rG  = – RT ln K
chemical reaction. or ∆rG  = – 2.303 RT log K (5.23)
(ii) Prediction of the useful work that could We also know that
be extracted from it.
So far we have considered free energy (5.24)
changes in irreversible reactions. Let us now For strongly endothermic reactions, the
examine the free energy changes in reversible value of ∆rH may be large and positive. In
reactions. such a case, value of K will be much smaller
‘Reversible’ under strict thermodynamic than 1 and the reaction is unlikely to
sense is a special way of carrying out form much product. In case of exothermic
a process such that system is at all reactions, ∆rH is large and negative, and ∆rG
times in perfect equilibrium with its is likely to be large and negative too. In such
surroundings. When applied to a chemical cases, K will be much larger than 1. We may
reaction, the term ‘reversible’ indicates expect strongly exothermic reactions to have a
that a given reaction can proceed in either large K, and hence can go to near completion.
direction simultaneously, so that a dynamic ∆rG also depends upon ∆rS, if the changes
equilibrium is set up. This means that the in the entropy of reaction is also taken into
reactions in both the directions should account, the value of K or extent of chemical
proceed with a decrease in free energy, which reaction will also be affected, depending upon
seems impossible. It is possible only if at whether ∆rS is positive or negative.
equilibrium the free energy of the system Using equation (5.24),
Table 5.4 Effect of Temperature on Spontaneity of Reactions

∆rH ∆rS ∆rG Description*

– + – Reaction spontaneous at all temperatures

– – – (at low T ) Reaction spontaneous at low temperature
– – + (at high T ) Reaction nonspontaneous at high temperature
+ + + (at low T ) Reaction nonspontaneous at low temperature
+ + – (at high T ) Reaction spontaneous at high temperature
+ – + (at all T ) Reaction nonspontaneous at all temperatures

* The term low temperature and high temperature are relative. For a particular reaction, high temperature could even mean
room temperature.

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 THERMODYNAMICS 163

(i) It is possible to obtain an estimate of ∆G

from the measurement of ∆H and ∆S,
 –13.6  10 3
J mol –1 
=
and then calculate K at any temperature 2.303 8.314 JK –1
mol –1
 298 K 
for economic yields of the products. = 2.38
(ii) If K is measured directly in the laboratory, Hence K = antilog 2.38 = 2.4 × 102.
value of ∆G at any other temperature Problem 5.14
can be calculated.
At 60°C, dinitrogen tetroxide is 50
Using equation (5.24), per cent dissociated. Calculate the
standard free energy change at this
temperature and at one atmosphere.
Problem 5.12
Calculate ∆rG for conversion of oxygen Solution
to ozone, 3/2 O2(g) → O3(g) at 298 K. if Kp N2O4(g) 2NO2(g)
for this conversion is 2.47 × 10–29.
If N 2O 4 is 50% dissociated, the mole
Solution fraction of both the substances is given
We know ∆rG = – 2.303 RT log Kp and by
R = 8.314 JK–1 mol–1 1 0.5 2  0.5
xN O  : x NO2 
Therefore, ∆rG = 2 4
1 0.5 1  0.5
– 2.303 (8.314 J K–1 mol–1) 0.5
× (298 K) (log 2.47 × 10–29) pN   1 atm, p NO 
2 O4 1.5 2

= 163000 J mol–1
1
= 163 kJ mol–1.  1 atm.
1.5
Problem 5.13
Find out the value of equilibrium constant The equilibrium constant Kp is given by
p 
2
for the following reaction at 298 K. NO2 1.5
Kp = 
p N 2 O4 (1.5)2 (0.5)
= 1.33 atm.
Standard Gibbs energy change, ∆rG at Since
the given temperature is –13.6 kJ mol–1.
∆rG = –RT ln Kp
Solution
∆rG = (– 8.314 JK–1 mol–1) × (333 K)
We know, log K =
× (2.303) × (0.1239)
= – 763.8 kJ mol –1

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 164 chemIstry

Summary

Thermodynamics deals with energy changes in chemical or physical processes and enables us to
study these changes quantitatively and to make useful predictions. For these purposes, we divide
the universe into the system and the surroundings. Chemical or physical processes lead to evolution
or absorption of heat (q), part of which may be converted into work (w). These quantities are related
through the first law of thermodynamics via ∆U = q + w. ∆U, change in internal energy, depends
on initial and final states only and is a state function, whereas q and w depend on the path and
are not the state functions. We follow sign conventions of q and w by giving the positive sign to
these quantities when these are added to the system. We can measure the transfer of heat from one
system to another which causes the change in temperature. The magnitude of rise in temperature
depends on the heat capacity (C) of a substance. Therefore, heat absorbed or evolved is q = C∆T.
Work can be measured by w = –pex∆V, in case of expansion of gases. Under reversible process, we
can put pex = p for infinitesimal changes in the volume making wrev = – p dV. In this condition, we
can use gas equation, pV = nRT.

At constant volume, w = 0, then ∆U = qV , heat transfer at constant volume. But in study of

chemical reactions, we usually have constant pressure. We define another state function enthalpy.
Enthalpy change, ∆H = ∆U + ∆ngRT, can be found directly from the heat changes at constant pressure,
∆H = qp.
There are varieties of enthalpy changes. Changes of phase such as melting, vaporization and
sublimation usually occur at constant temperature and can be characterized by enthalpy changes
which are always positive. Enthalpy of formation, combustion and other enthalpy changes can be
calculated using Hess’s law. Enthalpy change for chemical reactions can be determined by
r H   a 
f
i f  i

H products   bi  f H reactions 
and in gaseous state by
∆rH = Σ bond enthalpies of the reactants – Σ bond enthalpies of the products
First law of thermodynamics does not guide us about the direction of chemical
reactions i.e., what is the driving force of a chemical reaction. For isolated systems,
∆U = 0. We define another state function, S, entropy for this purpose. Entropy is a measure
of disorder or randomness. For a spontaneous change, total entropy change is positive.
Therefore, for an isolated system, ∆U = 0, ∆S > 0, so entropy change distinguishes a spontaneous
change, while energy change does not. Entropy changes can be measured by the equation
q rev q rev
∆S = for a reversible process. is independent of path.
T T
Chemical reactions are generally carried at constant pressure, so we define another state function
Gibbs energy, G, which is related to entropy and enthalpy changes of the system by the equation:
∆rG = ∆rH – T ∆rS
For a spontaneous change, ∆Gsys < 0 and at equilibrium, ∆Gsys = 0.
Standard Gibbs energy change is related to equilibrium constant by
∆rG = – RT ln K.
K can be calculated from this equation, if we know ∆ rG  which can be found from
. Temperature is an important factor in the equation. Many reactions which
are non-spontaneous at low temperature, are made spontaneous at high temperature for systems
having positive entropy of reaction.

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 THERMODYNAMICS 165

Exercises

5.1 Choose the correct answer. A thermodynamic state function is a quantity

(i) used to determine heat changes
(ii) whose value is independent of path
(iii) used to determine pressure volume work
(iv) whose value depends on temperature only.
5.2 For the process to occur under adiabatic conditions, the correct condition is:
(i) ∆T = 0
(ii) ∆p = 0
(iii) q=0
(iv) w=0
5.3 The enthalpies of all elements in their standard states are:
(i) unity
(ii) zero
(iii) <0
(iv) different for each element
5.4 ∆U of combustion of methane is – X kJ mol–1. The value of ∆H is


(i) = ∆U 
(ii) > ∆U 
(iii) < ∆U 
(iv) =0
5.5 The enthalpy of combustion of methane, graphite and dihydrogen at 298 K are,
–890.3 kJ mol–1 –393.5 kJ mol–1, and –285.8 kJ mol–1 respectively. Enthalpy of
formation of CH4(g) will be
(i) –74.8 kJ mol–1 (ii) –52.27 kJ mol–1
(iii) +74.8 kJ mol–1 (iv) +52.26 kJ mol–1.
5.6 A reaction, A + B → C + D + q is found to have a positive entropy change. The
reaction will be
(i) possible at high temperature
(ii) possible only at low temperature
(iii) not possible at any temperature
(v) possible at any temperature
5.7 In a process, 701 J of heat is absorbed by a system and 394 J of work is done by
the system. What is the change in internal energy for the process?
5.8 The reaction of cyanamide, NH2CN (s), with dioxygen was carried out in a bomb
calorimeter, and ∆U was found to be –742.7 kJ mol–1 at 298 K. Calculate enthalpy
change for the reaction at 298 K.
3
NH2CN(g) + O (g) → N2(g) + CO2(g) + H2O(l)
2 2

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 166 chemIstry

5.9 Calculate the number of kJ of heat necessary to raise the temperature of

60.0 g of aluminium from 35°C to 55°C. Molar heat capacity of Al is 24 J mol–1 K–1.
5.10 Calculate the enthalpy change on freezing of 1.0 mol of water at10.0°C to ice at
–10.0°C. ∆fusH = 6.03 kJ mol–1 at 0°C.
Cp [H2O(l)] = 75.3 J mol–1 K–1
Cp [H2O(s)] = 36.8 J mol–1 K–1
5.11 Enthalpy of combustion of carbon to CO2 is –393.5 kJ mol–1. Calculate the heat
released upon formation of 35.2 g of CO2 from carbon and dioxygen gas.
5.12 Enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are –110, – 393, 81
and 9.7 kJ mol–1 respectively. Find the value of ∆rH for the reaction:
N2O4(g) + 3CO(g) → N2O(g) + 3CO2(g)
5.13 Given
N2(g) + 3H2(g) → 2NH3(g); ∆rH = –92.4 kJ mol–1
What is the standard enthalpy of formation of NH3 gas?
5.14 Calculate the standard enthalpy of formation of CH3OH(l) from the following data:
3
CH3OH (l) + O (g) → CO2(g) + 2H2O(l) ; ∆rH = –726 kJ mol–1
2 2
C(graphite) + O2(g) → CO2(g) ; ∆cH = –393 kJ mol–1
1
H2(g) + O (g) → H2O(l); ∆f H = –286 kJ mol–1.
2 2
5.15 Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4 Cl(g)
and calculate bond enthalpy of C – Cl in CCl4(g).
∆vapH(CCl4) = 30.5 kJ mol–1.
∆fH (CCl4) = –135.5 kJ mol–1.
∆aH (C) = 715.0 kJ mol–1, where ∆aH is enthalpy of atomisation
∆aH (Cl2) = 242 kJ mol–1
5.16 For an isolated system, ∆U = 0, what will be ∆S ?
5.17 For the reaction at 298 K,
2A + B → C
∆H = 400 kJ mol–1 and ∆S = 0.2 kJ K–1 mol–1
At what temperature will the reaction become spontaneous considering ∆H and ∆S
to be constant over the temperature range.
5.18 For the reaction,
2 Cl(g) → Cl2(g), what are the signs of ∆H and ∆S ?
5.19 For the reaction
2 A(g) + B(g) → 2D(g)
∆U 
= –10.5 kJ and ∆S = –44.1 JK–1.
Calculate ∆G for the reaction, and predict whether the reaction may occur
spontaneously.

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 THERMODYNAMICS 167

5.20 The equilibrium constant for a reaction is 10. What will be the value of ∆G ?
R = 8.314 JK–1 mol–1, T = 300 K.
5.21 Comment on the thermodynamic stability of NO(g), given
1 1
N (g) + O (g) → NO(g); ∆rH = 90 kJ mol–1
2 2 2 2
1
NO(g) + O2(g) → NO2(g): ∆rH= –74 kJ mol–1
2
5.22 Calculate the entropy change in surroundings when 1.00 mol of H2O(l) is formed
under standard conditions. ∆f H = –286 kJ mol–1.

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 Unit 6

Equilibrium

Chemical equilibria are important in numerous biological

and environmental processes. For example, equilibria
involving O2 molecules and the protein hemoglobin play
After studying this unit you will be
a crucial role in the transport and delivery of O2 from
able to
our lungs to our muscles. Similar equilibria involving CO
• identify dynamic nature of molecules and hemoglobin account for the toxicity of CO.
equilibrium involved in physical
and chemical processes; When a liquid evaporates in a closed container,
• state the law of equilibrium; molecules with relatively higher kinetic energy escape
• explain characteristics of the liquid surface into the vapour phase and number of
equilibria involved in physical liquid molecules from the vapour phase strike the liquid
and chemical processes; surface and are retained in the liquid phase. It gives rise
• write expressions for equilibrium to a constant vapour pressure because of an equilibrium in
constants;
which the number of molecules leaving the liquid equals the
• establish a relationship between
Kp and Kc; number returning to liquid from the vapour. We say that
• explain various factors that the system has reached equilibrium state at this stage.
affect the equilibrium state of a However, this is not static equilibrium and there is a lot of
reaction; activity at the boundary between the liquid and the vapour.
• classify substances as acids or Thus, at equilibrium, the rate of evaporation is equal to the
bases according to Arrhenius, rate of condensation. It may be represented by
Bronsted-Lowry and Lewis
concepts; H2O (l) H2O (vap)
• classify acids and bases as
The double half arrows indicate that the processes
weak or strong in terms of their
ionization constants; in both the directions are going on simultaneously. The
• explain the dependence of degree mixture of reactants and products in the equilibrium state
of ionization on concentration is called an equilibrium mixture.
of the electrolyte and that of the
common ion; Equilibrium can be established for both physical
• describe pH scale for representing processes and chemical reactions. The reaction may be
hydrogen ion concentration; fast or slow depending on the experimental conditions and
• explain ionisation of water and the nature of the reactants. When the reactants in a closed
its duel role as acid and base; vessel at a particular temperature react to give products,
• describe ionic product (Kw ) and the concentrations of the reactants keep on decreasing,
pKw for water;
while those of products keep on increasing for some time
• appreciate use of buffer
after which there is no change in the concentrations
solutions;
• calculate solubility product
of either of the reactants or products. This stage of the
constant. system is the dynamic equilibrium and the rates of the
forward and reverse reactions become equal. It is due to

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 EQUILIBRIUM 169

this dynamic equilibrium stage that there is characteristic features. We observe that the
no change in the concentrations of various mass of ice and water do not change with
species in the reaction mixture. Based on the time and the temperature remains constant.
extent to which the reactions proceed to reach However, the equilibrium is not static.
the state of chemical equilibrium, these may The intense activity can be noticed at the
be classified in three groups. boundary between ice and water. Molecules
(i) The reactions that proceed nearly from the liquid water collide against ice and
to completion and only negligible adhere to it and some molecules of ice escape
concentrations of the reactants are into liquid phase. There is no change of mass
left. In some cases, it may not be even of ice and water, as the rates of transfer of
possible to detect these experimentally. molecules from ice into water and of reverse
transfer from water into ice are equal at
(ii) The reactions in which only small
atmospheric pressure and 273 K.
amounts of products are formed and
most of the reactants remain unchanged It is obvious that ice and water are in
at equilibrium stage. equilibrium only at particular temperature
and pressure. For any pure substance at
(iii) The reactions in which the concentrations
atmospheric pressure, the temperature at
of the reactants and products are
which the solid and liquid phases are at
comparable, when the system is in
equilibrium is called the normal melting point
equilibrium.
or normal freezing point of the substance. The
The extent of a reaction in equilibrium system here is in dynamic equilibrium and we
varies with the experimental conditions such can infer the following:
as concentrations of reactants, temperature, (i) Both the opposing processes occur
etc. Optimisation of the operational conditions simultaneously.
is very important in industry and laboratory (ii) Both the processes occur at the same
so that equilibrium is favorable in the rate so that the amount of ice and water
direction of the desired product. Some remains constant.
important aspects of equilibrium involving
physical and chemical processes are dealt in 6.1.2 Liquid-Vapour Equilibrium
this unit along with the equilibrium involving This equilibrium can be better understood if
ions in aqueous solutions which is called as we consider the example of a transparent box
ionic equilibrium. carrying a U-tube with mercury (manometer).
Drying agent like anhydrous calcium chloride
6.1 E Q U IL IBRI U M IN P H Y S I C A L
(or phosphorus penta-oxide) is placed for
PROCESSES
a few hours in the box. After removing the
The characteristics of system at equilibrium drying agent by tilting the box on one side, a
are better understood if we examine some watch glass (or petri dish) containing water
physical processes. The most familiar examples is quickly placed inside the box. It will be
are phase transformation processes, e.g., observed that the mercury level in the right
solid liquid limb of the manometer slowly increases and
liquid gas finally attains a constant value, that is, the
solid gas pressure inside the box increases and reaches
a constant value. Also the volume of water in
6.1.1 Solid-Liquid Equilibrium
the watch glass decreases (Fig. 6.1). Initially
Ice and water kept in a perfectly insulated there was no water vapour (or very less) inside
thermos flask (no exchange of heat between its the box. As water evaporated the pressure in
contents and the surroundings) at 273K and the box increased due to addition of water
the atmospheric pressure are in equilibrium molecules into the gaseous phase inside
state and the system shows interesting the box. The rate of evaporation is constant.

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 170 chemistry

Fig. 6.1 Measuring equilibrium vapour pressure of water at a constant temperature

However, the rate of increase in pressure vapour to liquid state is much less than the
decreases with time due to condensation rate of evaporation. These are open systems
of vapour into water. Finally it leads to an and it is not possible to reach equilibrium in
equilibrium condition when there is no net an open system.
evaporation. This implies that the number
Water and water vapour are in equilibrium
of water molecules from the gaseous state
into the liquid state also increases till the position at atmospheric pressure (1.013 bar)
equilibrium is attained i.e., and at 100°C in a closed vessel. The boiling
point of water is 100°C at 1.013 bar pressure.
rate of evaporation= rate of condensation
For any pure liquid at one atmospheric
H2O(l) H2O (vap)
pressure (1.013 bar), the temperature
At equilibrium the pressure exerted by at which the liquid and vapours are at
the water molecules at a given temperature equilibrium is called normal boiling point of
remains constant and is called the equilibrium the liquid. Boiling point of the liquid depends
vapour pressure of water (or just vapour on the atmospheric pressure. It depends on
pressure of water); vapour pressure of water the altitude of the place; at high altitude the
increases with temperature. If the above boiling point decreases.
experiment is repeated with methyl alcohol,
acetone and ether, it is observed that different 6.1.3 Solid – Vapour Equilibrium
liquids have different equilibrium vapour
Let us now consider the systems where solids
pressures at the same temperature, and the
sublime to vapour phase. If we place solid
liquid which has a higher vapour pressure is
iodine in a closed vessel, after sometime
more volatile and has a lower boiling point.
the vessel gets filled up with violet vapour
If we expose three watch glasses containing and the intensity of colour increases with
separately 1mL each of acetone, ethyl alcohol, time. After certain time the intensity of
and water to atmosphere and repeat the colour becomes constant and at this stage
experiment with different volumes of the
equilibrium is attained. Hence solid iodine
liquids in a warmer room, it is observed
sublimes to give iodine vapour and the iodine
that in all such cases the liquid eventually
vapour condenses to give solid iodine. The
disappears and the time taken for complete
equilibrium can be represented as,
evaporation depends on (i) the nature of the
liquid, (ii) the amount of the liquid and (iii) the I2(solid) I2 (vapour)
temperature. When the watch glass is open Other examples showing this kind of
to the atmosphere, the rate of evaporation equilibrium are,
remains constant but the molecules are
dispersed into large volume of the room. As Camphor (solid) Camphor (vapour)
a consequence the rate of condensation from NH4Cl (solid) NH4Cl (vapour)

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 EQUILIBRIUM 171

6.1.4 Equilibrium Involving Dissolution pressure of the gas above the solvent.
of Solid or Gases in Liquids This amount decreases with increase of
Solids in liquids temperature. The soda water bottle is sealed
under pressure of gas when its solubility in
We know from our experience that we can
water is high. As soon as the bottle is opened,
dissolve only a limited amount of salt or
some of the dissolved carbon dioxide gas
sugar in a given amount of water at room
escapes to reach a new equilibrium condition
temperature. If we make a thick sugar syrup
required for the lower pressure, namely its
solution by dissolving sugar at a higher
partial pressure in the atmosphere. This is
temperature, sugar crystals separate out if we
how the soda water in bottle when left open
cool the syrup to the room temperature. We call
to the air for some time, turns ‘flat’. It can be
it a saturated solution when no more of solute
generalised that:
can be dissolved in it at a given temperature.
The concentration of the solute in a saturated (i) For solid liquid equilibrium, there is
solution depends upon the temperature. In only one temperature (melting point) at
a saturated solution, a dynamic equilibrium 1 atm (1.013 bar) at which the two
exits between the solute molecules in the solid phases can coexist. If there is no
state and in the solution: exchange of heat with the surroundings,
the mass of the two phases remains
Sugar (solution) Sugar (solid), and
constant.
the rate of dissolution of sugar = rate of
crystallisation of sugar. (ii) For liquid vapour equilibrium, the
vapour pressure is constant at a given
Equality of the two rates and dynamic
temperature.
nature of equilibrium has been confirmed with
the help of radioactive sugar. If we drop some (iii) For dissolution of solids in liquids,
radioactive sugar into saturated solution of the solubility is constant at a given
non-radioactive sugar, then after some time temperature.
radioactivity is observed both in the solution (iv) For dissolution of gases in liquids,
and in the solid sugar. Initially there were no the concentration of a gas in liquid
radioactive sugar molecules in the solution is proportional to the pressure
but due to dynamic nature of equilibrium, (concentration) of the gas over the liquid.
there is exchange between the radioactive These observations are summarised in
and non-radioactive sugar molecules between Table 6.1
the two phases. The ratio of the radioactive Table 6.1 Some Features of Physical Equilibria
to non-radioactive molecules in the solution
increases till it attains a constant value. Process Conclusion
Liquid Vapour p H 2O constant at given
Gases in liquids temperature
H2O (l) H2O (g)
When a soda water bottle is opened, some of
Solid Liquid Melting point is fixed at
the carbon dioxide gas dissolved in it fizzes constant pressure
out rapidly. The phenomenon arises due H2O (s) H2O (l)
to difference in solubility of carbon dioxide Solute(s) Solute Concentration of solute
at different pressures. There is equilibrium (solution) in solution is constant
between the molecules in the gaseous state Sugar(s) Sugar at a given temperature
and the molecules dissolved in the liquid (solution)
under pressure i.e.,
Gas(g) Gas (aq) [gas(aq)]/[gas(g)] is
CO2 (gas) CO2 (in solution) constant at a given
This equilibrium is governed by Henry’s temperature
CO2(g) CO2(aq)
law, which states that the mass of a gas [CO2(aq)]/[CO2(g)] is
dissolved in a given mass of a solvent at constant at a given
any temperature is proportional to the temperature

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 172 chemistry

6.1.5 General Characteristics of

Equilibria Involving Physical
Processes
For the physical processes discussed above,
following characteristics are common to the
system at equilibrium:
(i) Equilibrium is possible only in a closed
system at a given temperature.
(ii) Both the opposing processes occur at
the same rate and there is a dynamic
but stable condition.
(iii) All measurable properties of the system
remain constant.
(iv) When equilibrium is attained for a
physical process, it is characterised by Fig. 6.2 Attainment of chemical equilibrium.
constant value of one of its parameters
at a given temperature. Table 6.1 lists Eventually, the two reactions occur at the
such quantities. same rate and the system reaches a state of
(v) The magnitude of such quantities at any equilibrium.
stage indicates the extent to which the Similarly, the reaction can reach the state
physical process has proceeded before of equilibrium even if we start with only C and
reaching equilibrium. D; that is, no A and B being present initially,
as the equilibrium can be reached from either
6.2 EQUILIBRIUM IN CHEMICAL direction.
PROCESSES – DYNAMIC
EQUILIBRIUM The dynamic nature of chemical
equilibrium can be demonstrated in the
Analogous to the physical systems chemical synthesis of ammonia by Haber’s process.
reactions also attain a state of equilibrium. In a series of experiments, Haber started
These reactions can occur both in forward with known amounts of dinitrogen and
and backward directions. When the rates of dihydrogen maintained at high temperature
the forward and reverse reactions become and pressure and at regular intervals
equal, the concentrations of the reactants determined the amount of ammonia present.
and the products remain constant. This He was successful in determining also the
is the stage of chemical equilibrium. This concentration of unreacted dihydrogen and
equilibrium is dynamic in nature as it consists dinitrogen. Fig. 6.4 (page 174) shows that after
of a forward reaction in which the reactants a certain time the composition of the mixture
give product(s) and reverse reaction in which remains the same even though some of the
product(s) gives the original reactants. reactants are still present. This constancy in
For a better comprehension, let us consider composition indicates that the reaction has
a general case of a reversible reaction, reached equilibrium. In order to understand
A+B C+D the dynamic nature of the reaction, synthesis
of ammonia is carried out with exactly the
With passage of time, there is same starting conditions (of partial pressure
accumulation of the products C and D and and temperature) but using D2 (deuterium)
depletion of the reactants A and B (Fig. 6.2). in place of H2. The reaction mixtures starting
This leads to a decrease in the rate of either with H2 or D2 reach equilibrium with
forward reaction and an increase in the rate the same composition, except that D2 and
of the reverse reaction, ND3 are present instead of H2 and NH3. After

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 EQUILIBRIUM 173

Dynamic Equilibrium – A Student’s Activity

Equilibrium whether in a physical or in a chemical system, is always of dynamic nature. This can
be demonstrated by the use of radioactive isotopes. This is not feasible in a school laboratory.
However this concept can be easily comprehended by performing the following activity. The activity
can be performed in a group of 5 or 6 students.
Take two 100mL measuring cylinders (marked as 1 and 2) and two glass tubes each of
30 cm length. Diameter of the tubes may be same or different in the range of 3-5mm. Fill
nearly half of the measuring cylinder-1 with coloured water (for this purpose add a crystal
of potassium permanganate to water) and keep second cylinder (number 2) empty.
Put one tube in cylinder 1 and second in cylinder 2. Immerse one tube in cylinder 1,
close its upper tip with a finger and transfer the coloured water contained in its lower portion to
cylinder 2. Using second tube, kept in 2nd cylinder, transfer the coloured water in a similar manner
from cylinder 2 to cylinder 1. In this way keep on transferring coloured water using the two glass
tubes from cylinder 1 to 2 and from 2 to 1 till you notice that the level of coloured water in both
the cylinders becomes constant.
If you continue intertransferring coloured solution between the cylinders, there will not be
any further change in the levels of coloured water in two cylinders. If we take analogy of ‘level’ of
coloured water with ‘concentration’ of reactants and products in the two cylinders, we can say
the process of transfer, which continues even after the constancy of level, is indicative of dynamic
nature of the process. If we repeat the experiment taking two tubes of different diameters we find
that at equilibrium the level of coloured water in two cylinders is different. How far diameters are
responsible for change in levels in two cylinders? Empty cylinder (2) is an indicator of no product
in it at the beginning.

1 2 1 2

(a) (b)
Fig.6.3 Demonstrating dynamic nature of equilibrium. (a) initial stage (b) final stage after the
equilibrium is attained.

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 174 chemistry

2NH3(g) N2(g) + 3H2(g)

Similarly let us consider the reaction,
H 2 (g) + I 2 (g) 2HI(g). If we start with
equal initial concentration of H2 and I2, the
reaction proceeds in the forward direction
and the concentration of H2 and I2 decreases
while that of HI increases, until all of these
become constant at equilibrium (Fig. 6.5). We
can also start with HI alone and make the
reaction to proceed in the reverse direction;
the concentration of HI will decrease and
concentration of H2 and I2 will increase until
they all become constant when equilibrium is
reached (Fig. 6.5). If total number of H and I
atoms are same in a given volume, the same
equilibrium mixture is obtained whether we
Fig. 6.4 Depiction of equilibrium for the reaction
start it from pure reactants or pure product.
N 2  g   3H 2  g  2NH3  g 

equilibrium is attained, these two mixtures

(H 2, N 2, NH 3 and D 2, N 2, ND 3) are mixed
together and left for a while. Later, when
this mixture is analysed, it is found that the
concentration of ammonia is just the same
as before. However, when this mixture is
analysed by a mass spectrometer, it is found
that ammonia and all deuterium containing
forms of ammonia (NH3, NH2D, NHD2 and
ND3) and dihydrogen and its deutrated forms
(H2, HD and D2) are present. Thus one can
conclude that scrambling of H and D atoms in
the molecules must result from a continuation
of the forward and reverse reactions in the
mixture. If the reaction had simply stopped
Fig. 6.5 Chemical equilibrium in the reaction H2(g)
when they reached equilibrium, then there
+ I2(g) 2HI(g) can be attained from
would have been no mixing of isotopes in either direction
this way.
6.3 LAW OF CHEMICAL EQUILIBRIUM
Use of isotope (deuterium) in the formation AND EQUILIBRIUM CONSTANT
of ammonia clearly indicates that chemical
A mixture of reactants and products in the
reactions reach a state of dynamic
equilibrium state is called an equilibrium
equilibrium in which the rates of forward
mixture. In this section we shall address a
and reverse reactions are equal and there
number of important questions about the
is no net change in composition.
composition of equilibrium mixtures: What is
Equilibrium can be attained from both the relationship between the concentrations
sides, whether we start reaction by taking, of reactants and products in an equilibrium
H2(g) and N2(g) and get NH3(g) or by taking mixture? How can we determine equilibrium
NH3(g) and decomposing it into N2(g) and H2(g). concentrations from initial concentrations?
N2(g) + 3H2(g) 2NH3(g) What factors can be exploited to alter the

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 EQUILIBRIUM 175

composition of an equilibrium mixture? The Six sets of experiments with varying initial
last question in particular is important when conditions were performed, starting with only
choosing conditions for synthesis of industrial gaseous H2 and I2 in a sealed reaction vessel
chemicals such as H2, NH3, CaO etc. in first four experiments (1, 2, 3 and 4) and
To answer these questions, let us consider only HI in other two experiments (5 and 6).
a general reversible reaction: Experiment 1, 2, 3 and 4 were performed
A+B C+D taking different concentrations of H2 and / or
where A and B are the reactants, C and D I2, and with time it was observed that intensity
are the products in the balanced chemical of the purple colour remained constant and
equation. On the basis of experimental studies equilibrium was attained. Similarly, for
of many reversible reactions, the Norwegian experiments 5 and 6, the equilibrium was
chemists Cato Maximillian Guldberg and attained from the opposite direction.
Peter Waage proposed in 1864 that the Data obtained from all six sets of
concentrations in an equilibrium mixture experiments are given in Table 6.2.
are related by the following equilibrium
equation, It is evident from the experiments 1, 2,
3 and 4 that number of moles of dihydrogen
Kc 
CD         (6.1) reacted = number of moles of iodine reacted
 A B  = ½ (number of moles of HI formed). Also,
(6.1) where Kc is the equilibrium constant and experiments 5 and 6 indicate that,
the expression on the right side is called the [H2(g)]eq = [I2(g)]eq
equilibrium constant expression.
The equilibrium equation is also known as Knowing the above facts, in order
the law of mass action because in the early to establish a relationship between
days of chemistry, concentration was called concentrations of the reactants and products,
“active mass”. In order to appreciate their several combinations can be tried. Let us
work better, let us consider reaction between consider the simple expression,
gaseous H2 and I2 carried out in a sealed vessel [HI(g)]eq / [H2(g)]eq [I2(g)]eq
at 731K.
H2(g) + I2(g)   2HI(g) It can be seen from Table 6.3 that if we
1 mol 1 mol 2 mol put the equilibrium concentrations of the
reactants and products, the above expression

Table 6.2 Initial and Equilibrium Concentrations of H2, I2 and HI

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 176 chemistry

Table 6.3 Expression Involving the The equilibrium constant for a general
Equilibrium Concentration of reaction,
Reactants
aA + bB cC + dD
H2(g) + I2(g) 2HI(g)
is expressed as,
Kc = [C]c[D]d / [A]a[B]b (6.4)

where [A], [B], [C] and [D] are the equilibrium

concentrations of the reactants and products.
Equilibrium constant for the reaction,
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) is written
as
Kc = [NO]4[H2O]6 / [NH3]4 [O2]5
Molar concentration of different species is
is far from constant. However, if we consider indicated by enclosing these in square bracket
the expression, and, as mentioned above, it is implied that
[HI(g)]2eq / [H2(g)]eq [I2(g)]eq these are equilibrium concentrations. While
writing expression for equilibrium constant,
we find that this expression gives constant
symbol for phases (s, l, g) are generally ignored.
value (as shown in Table 6.3) in all the six
cases. It can be seen that in this expression Let us write equilibrium constant for the
the power of the concentration for reactants reaction, H2(g) + I2(g) 2HI(g) (6.5)
and products are actually the stoichiometric
as, Kc = [HI]2 / [H2] [I2] = x (6.6)
coefficients in the equation for the chemical
reaction. Thus, for the reaction H2(g) + I2(g) The equilibrium constant for the reverse
2HI(g), following equation 6.1, the equilibrium reaction, 2HI(g) H2(g) + I2(g), at the same
constant Kc is written as, temperature is,
Kc = [HI(g)]eq2 / [H2(g)]eq [I2(g)]eq (6.2) K′c = [H2] [I2] / [HI]2 = 1/ x = 1 / Kc (6.7)
Generally the subscript ‘eq’ (used for Thus, K′c = 1 / Kc (6.8)
equilibrium) is omitted from the concentration Equilibrium constant for the reverse
terms. It is taken for granted that the reaction is the inverse of the equilibrium
concentrations in the expression for Kc are constant for the reaction in the forward
equilibrium values. We, therefore, write, direction.
Kc = [HI(g)]2 / [H2(g)] [I2(g)] (6.3) If we change the stoichiometric coefficients
in a chemical equation by multiplying
The subscript ‘c’ indicates that K c is
throughout by a factor then we must make
expressed in concentrations of mol L–1.
sure that the expression for equilibrium
At a given temperature, the product of constant also reflects that change. For
concentrations of the reaction products example, if the reaction (6.5) is written as,
raised to the respective stoichiometric
coefficient in the balanced chemical ½ H2(g) + ½ I2(g) HI(g) (6.9)
equation divided by the product of the equilibrium constant for the above
concentrations of the reactants raised to reaction is given by
their individual stoichiometric coefficients K″c = [HI] / [H2]1/2[I2]1/2 = {[HI]2 / [H2][I2]}1/2
has a constant value. This is known as
the Equilibrium Law or Law of Chemical = x1/2 = Kc1/2 (6.10)
Equilibrium. On multiplying the equation (6.5) by n, we get

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 EQUILIBRIUM 177

nH2(g) + nI2(g) D 2nHI(g) (6.11)

Therefore, equilibrium constant for the N2(g) + O2(g) 2NO(g)
reaction is equal to Kc n. These findings are Solution
summarised in Table 6.4. It should be noted
that because the equilibrium constants Kc For the reaction equilibrium constant, Kc
and K ′c have different numerical values, it is can be written as,
2
important to specify the form of the balanced NO
Kc =
chemical equation when quoting the value of N 2 O2
an equilibrium constant. 2
2.8 10–3M
Table 6.4 Relations between Equilibrium =
Constants for a General Reaction 3.0 10 3 M 4.2 10 3 M
and its Multiples.
= 0.622
Chemical equation Equilibrium
constant
aA+bB c C + dD Kc
6.4 HOMOGENEOUS EQUILIBRIA
cC+dD aA+bB K′c =(1/Kc ) In a homogeneous system, all the reactants
and products are in the same phase.
na A + nb B ncC + ndD K′″c = (Kcn )
For example, in the gaseous reaction,
N 2(g) + 3H 2(g) 2NH 3(g), reactants and
products are in the homogeneous phase.
Problem 6.1
Similarly, for the reactions,
The following concentrations were CH3COOC2H5 (aq) + H2O (l) CH3COOH (aq)
obtained for the formation of NH3 from + C2H5OH (aq)
N 2 and H 2 at equilibrium at 500K.
[N2] = 1.5 × 10–2M. [H2] = 3.0 ×10–2 M and and, Fe3+ (aq) + SCN–(aq) Fe(SCN)2+ (aq)
[NH3] = 1.2 ×10–2M. Calculate equilibrium all the reactants and products are in
constant. homogeneous solution phase. We shall now
consider equilibrium constant for some
Solution
homogeneous reactions.
The equilibrium constant for the reaction,
N2(g) + 3H2(g) 2NH3(g) can be written as, 6.4.1 Equilibrium Constant in Gaseous
Systems
 NH3  g 
2
So far we have expressed equilibrium
Kc = constant of the reactions in terms of molar
 N 2  g  H2  g 
3
concentration of the reactants and products,
and used symbol, Kc for it. For reactions
=
1.2  10  2 2
involving gases, however, it is usually more
1.5  10  3.0  10 
2 2 3
convenient to express the equilibrium
constant in terms of partial pressure.
= 0.106 × 104 = 1.06 × 103 The ideal gas equation is written as,
pV = nRT
Problem 6.2
n
At equilibrium, the concentrations of ⇒ p = RT
N 2=3.0 × 10 –3M, O 2 = 4.2 × 10 –3M and V
NO= 2.8 × 10–3M in a sealed vessel at 800K. Here, p is the pressure in Pa, n is the number
What will be Kc for the reaction of moles of the gas, V is the volume in m3 and
T is the temperature in Kelvin

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 178 chemistry

Therefore,
n/V is concentration expressed in mol/m3  NH3 ( g ) [RT ]
2 −2

=  = K c ( RT )
−2
If concentration c, is in mol/L or mol/dm3,
 N 2 ( g ) H 2 ( g )
3
and p is in bar then
p = cRT,
or K p = K c ( RT ) (6.14)
−2
We can also write p = [gas]RT.
Here, R= 0.0831 bar litre/mol K Similarly, for a general reaction
At constant temperature, the pressure of aA + bB cC + dD
the gas is proportional to its concentration i.e.,
p ∝ [gas]
Kp =
( p )( p ) [C] [D] ( RT )(
C
c

=D
d c d c +d )

For reaction in equilibrium ( p )( p ) [ A ] [B] (RT )(

a
A
b
B
a b a +b )

H2(g) + I2(g) 2HI(g)

We can write either [ C ] [D]
c d

RT )
(c + d ) −(a +b )
b (
=
HI ( g )
2
[ A ] [B ]
a

Kc =
H2 ( g ) I2 ( g )
[ C ] [D]
c d

RT )
∆n
= K c ( RT )
∆n
b (
= (6.15)
or K c =
( p HI ) 2

(6.12)
[ A ] [B ]
a

( p )( p )
H2 I2
where ∆n = (number of moles of gaseous
products) – (number of moles of gaseous
Further, since p HI = HI ( g ) RT reactants) in the balanced chemical equation.
It is necessary that while calculating the value
pI2 = I2 ( g ) RT of Kp, pressure should be expressed in bar
p H2 = H2 ( g ) RT because standard state for pressure is 1 bar.
We know from Unit 1 that :
Therefore, 1pascal, Pa=1Nm–2, and 1bar = 105 Pa
HI ( g ) [RT ] Kp values for a few selected reactions at
( pHI )2
2 2

Kp = = different temperatures are given in Table 6.5

( p )( p )
H2 I2
H2 ( g ) RT . I2 ( g ) RT
Table 6.5 Equilibrium Constants, Kp for
HI ( g )
2
a Few Selected Reactions
= = Kc (6.13)
H2 ( g ) I2 ( g )
In this example, K p = K c i.e., both
equilibrium constants are equal. However,
this is not always the case. For example in
reaction
N2(g) + 3H2(g) 2NH3(g)

(p )
2
NH 3
Kp =
( p )( p )
3
N2 H2

Problem 6.3
 NH3 ( g ) [RT ]
2 2

= PCl5, PCl3 and Cl2 are at equilibrium at 500

 N 2 ( g ) RT . H 2 ( g ) (RT )
3 3
K and having concentration 1.59M PCl3,
1.59M Cl2 and 1.41 M PCl5.

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 EQUILIBRIUM 179

Calculate Kc for the reaction, the value 0.194 should be neglected because
PCl5 PCl3 + Cl2 it will give concentration of the reactant
Solution which is more than initial concentration.
The equilibrium constant Kc for the above Hence the equilibrium concentrations are,
reaction can be written as, [CO2] = [H2-] = x = 0.067 M

Kc 
PCl  Cl   1.59
3 2
2

 1.79
[CO] = [H2O] = 0.1 – 0.067 = 0.033 M
PCl  5 1.41 Problem 6.5
Problem 6.4 For the equilibrium,
The value of K c = 4.24 at 800K for the 2NOCl(g) 2NO(g) + Cl2(g)
reaction, the value of the equilibrium constant, Kc is
CO (g) + H2O (g) CO2 (g) + H2 (g) 3.75 × 10 –6 at 1069 K. Calculate the Kp for
Calculate equilibrium concentrations of CO2, the reaction at this temperature?
H2, CO and H2O at 800 K, if only CO and
H2O are present initially at concentrations Solution
of 0.10M each.
We know that,
Solution Kp = Kc(RT)∆n
For the reaction, For the above reaction,
CO (g) + H2O (g) CO2 (g) + H2 (g) ∆n = (2+1) – 2 = 1
Kp = 3.75 ×10–6 (0.0831 × 1069)
Initial concentration:
Kp = 0.033
0.1M 0.1M 0 0
Let x mole per litre of each of the product
be formed. 6.5 HETEROGENEOUS EQUILIBRIA
At equilibrium: Equilibrium in a system having more than one
(0.1-x) M (0.1-x) M xM xM phase is called heterogeneous equilibrium.
The equilibrium between water vapour and
where x is the amount of CO2 and H2 at
equilibrium. liquid water in a closed container is an
example of heterogeneous equilibrium.
Hence, equilibrium constant can be written
as, H2O(l) H2O(g)
Kc = x2/(0.1-x)2 = 4.24 In this example, there is a gas phase and
x2 = 4.24(0.01 + x2-0.2x) a liquid phase. In the same way, equilibrium
x2 = 0.0424 + 4.24x2-0.848x between a solid and its saturated solution,
3.24x2 – 0.848x + 0.0424 = 0 Ca(OH)2 (s) + (aq) Ca2+ (aq) + 2OH–(aq)
a = 3.24, b = – 0.848, c = 0.0424 is a heterogeneous equilibrium.
(for quadratic equation ax2 + bx + c = 0, Heterogeneous equilibria often involve

x
 b  b2  4ac  pure solids or liquids. We can simplify
equilibrium expressions for the heterogeneous
2a equilibria involving a pure liquid or a pure
x = 0.848±√(0.848)2– 4(3.24)(0.0424)/ solid, as the molar concentration of a pure
solid or liquid is constant (i.e., independent
(3.24×2)
of the amount present). In other words if a
x = (0.848 ± 0.4118)/ 6.48
substance ‘X’ is involved, then [X(s)] and [X(l)]
x1 = (0.848 – 0.4118)/6.48 = 0.067 are constant, whatever the amount of ‘X’ is
x2 = (0.848 + 0.4118)/6.48 = 0.194 taken. Contrary to this, [X(g)] and [X(aq)] will

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 180 chemistry

vary as the amount of X in a given volume This shows that at a particular

varies. Let us take thermal dissociation of temperature, there is a constant concentration
calcium carbonate which is an interesting and or pressure of CO2 in equilibrium with CaO(s)
important example of heterogeneous chemical and CaCO3(s). Experimentally it has been
equilibrium. found that at 1100 K, the pressure of CO2
in equilibrium with CaCO3(s) and CaO(s), is
CaCO3 (s) CaO (s) + CO2 (g) (6.16) 2.0 ×105 Pa. Therefore, equilibrium constant
On the basis of the stoichiometric equation, at 1100K for the above reaction is:
we can write, Kp = PCO2 = 2 × 105 Pa/105 Pa = 2.00
CaO  s  CO2  g  Similarly, in the equilibrium between
Kc 
CaCO3  s  nickel, carbon monoxide and nickel carbonyl
(used in the purification of nickel),
Since [CaCO3(s)] and [CaO(s)] are both
constant, therefore modified equilibrium Ni (s) + 4 CO (g) Ni(CO)4 (g),
constant for the thermal decomposition of the equilibrium constant is written as
calcium carbonate will be
 Ni CO 4 
K´c = [CO2(g)] (6.17) Kc  
or Kp = pCO (6.18) CO4
2

It must be remembered that for the

existence of heterogeneous equilibrium pure
Units of Equilibrium Constant solids or liquids must also be present (however
The value of equilibrium constant Kc can be small the amount may be) at equilibrium, but
calculated by substituting the concentration their concentrations or partial pressures do
terms in mol/L and for Kp partial pressure not appear in the expression of the equilibrium
is substituted in Pa, kPa, bar or atm. This constant. In the reaction,
results in units of equilibrium constant based Ag2O(s) + 2HNO3(aq) 2AgNO3(aq) +H2O(l)
on molarity or pressure, unless the exponents
of both the numerator and denominator are
 AgNO 
2
3
same. Kc =
HNO 
2
For the reactions, 3
H2(g) + I2(g) 2HI, Kc and Kp have no
unit.
N2O4(g) 2NO2 (g), Kc has unit mol/L
and Kp has unit bar Problem 6.6
Equilibrium constants can also be The value of Kp for the reaction,
expressed as dimensionless quantities if the CO2 (g) + C (s) 2CO (g)
standard state of reactants and products is 3.0 at 1000 K. If initially PCO = 0.48
2
are specified. For a pure gas, the standard bar and PCO = 0 bar and pure graphite is
state is 1bar. Therefore a pressure of 4 bar present, calculate the equilibrium partial
in standard state can be expressed as 4 pressures of CO and CO2.
bar/1 bar = 4, which is a dimensionless
number. Standard state (c0) for a solute is 1 Solution
molar solution and all concentrations can be For the reaction,
measured with respect to it. The numerical
value of equilibrium constant depends on the
let ‘x’ be the decrease in pressure of CO2,
standard state chosen. Thus, in this system
then
both Kp and Kc are dimensionless quantities CO2(g) + C(s) 2CO(g)
but have different numerical values due to Initial
different standard states. pressure: 0.48 bar 0

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 EQUILIBRIUM 181

5. The equilibrium constant K for a reaction

At equilibrium: is related to the equilibrium constant
(0.48 – x)bar 2x bar of the corresponding reaction, whose
equation is obtained by multiplying or
pC2 O dividing the equation for the original
Kp =
pC O2 reaction by a small integer.

Kp = (2x)2/(0.48 – x) = 3 Let us consider applications of equilibrium

constant to:
4x2 = 3(0.48 – x)
• predict the extent of a reaction on the
4x2 = 1.44 – x basis of its magnitude,
4x2 + 3x – 1.44 = 0
• predict the direction of the reaction, and
a = 4, b = 3, c = –1.44
•
b  
calculate equilibrium concentrations.
b2  4ac
x 6.6.1 Predicting the Extent of a
2a Reaction
= [–3 ± √(3) – 4(4)(–1.44)]/2 × 4
2 The numerical value of the equilibrium
= (–3 ± 5.66)/8 constant for a reaction indicates the extent
of the reaction. But it is important to note
= (–3 + 5.66)/8 (as value of x cannot be that an equilibrium constant does not give
negative hence we neglect that value)
any information about the rate at which
x = 2.66/8 = 0.33 the equilibrium is reached. The magnitude
The equilibrium partial pressures are, of Kc or Kp is directly proportional to the
concentrations of products (as these appear
pCO = 2x = 2 × 0.33 = 0.66 bar
2 in the numerator of equilibrium constant
pCO = 0.48 – x = 0.48 – 0.33 = 0.15 bar expression) and inversely proportional to the
2
concentrations of the reactants (these appear
6.6 APPLICATIONS OF EQUILIBRIUM in the denominator). This implies that a high
CONSTANTS value of K is suggestive of a high concentration
of products and vice-versa.
Before considering the applications of
equilibrium constants, let us summarise the We can make the following generalisations
important features of equilibrium constants concerning the composition of equilibrium
as follows: mixtures:
1. Expression for equilibrium constant is • If Kc > 103, products predominate over
applicable only when concentrations of reactants, i.e., if Kc is very large, the
the reactants and products have attained reaction proceeds nearly to completion.
constant value at equilibrium state. Consider the following examples:
2. The value of equilibrium constant is (a) The reaction of H 2 with O 2 at 500 K
independent of initial concentrations of has a very large equilibrium constant,
the reactants and products. Kc = 2.4 × 1047.
3. Equilibrium constant is temperature (b) H2(g) + Cl 2(g) 2HCl(g) at 300K has
dependent having one unique value for Kc = 4.0 × 1031.
a particular reaction represented by a (c) H 2(g) + Br 2(g) 2HBr (g) at 300 K,
balanced equation at a given temperature. Kc = 5.4 × 1018
4. The equilibrium constant for the reverse
• If Kc < 10–3, reactants predominate over
reaction is equal to the inverse of the
products, i.e., if Kc is very small, the
equilibrium constant for the forward
reaction proceeds rarely. Consider the
reaction. following examples:

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 182 chemistry

(a) The decomposition of H2O into H2 and If Qc = Kc, the reaction mixture is already
O2 at 500 K has a very small equilibrium at equilibrium.
constant, Kc = 4.1 × 10 –48 Consider the gaseous reaction of H 2
(b) N2(g) + O2(g) 2NO(g), with I2,
at 298 K has Kc = 4.8 ×10 – 31. H2(g) + I2(g) 2HI(g); Kc = 57.0 at 700 K.
• If K c is in the range of 10 – 3 to 10 3 , Suppose we have molar concentrations
appreciable concentrations of both [H2]t=0.10M, [I2]t = 0.20 M and [HI]t = 0.40 M.
reactants and products are present. (the subscript t on the concentration symbols
Consider the following examples: means that the concentrations were measured
(a) For reaction of H2 with I2 to give HI, at some arbitrary time t, not necessarily at
equilibrium).
Kc = 57.0 at 700K.
Thus, the reaction quotient, Qc at this
(b) Also, gas phase decomposition of N2O4
stage of the reaction is given by,
to NO2 is another reaction with a value
Qc = [HI]t2 / [H2]t [I2]t = (0.40)2/ (0.10)×(0.20)
of K c = 4.64 × 10 –3 at 25°C which is
neither too small nor too large. Hence, = 8.0
equilibrium mixtures contain appreciable Now, in this case, Qc (8.0) does not equal
concentrations of both N2O4 and NO2. Kc (57.0), so the mixture of H2(g), I2(g) and HI(g)
These generarlisations are illustrated in is not at equilibrium; that is, more H2(g) and
Fig. 6.6 I2(g) will react to form more HI(g) and their
concentrations will decrease till Qc = Kc.
The reaction quotient, Q c is useful in
predicting the direction of reaction by
comparing the values of Qc and Kc.
Thus, we can make the following
generalisations concerning the direction of
Fig.6.6 Dependence of extent of reaction on Kc the reaction (Fig. 6.7) :

6.6.2 Predicting the Direction of the

Reaction
The equilibrium constant helps in predicting
the direction in which a given reaction will
proceed at any stage. For this purpose,
we calculate the reaction quotient Q.
The reaction quotient, Q (Q c with molar
concentrations and QP with partial pressures) Fig. 6.7 Predicting the direction of the reaction
is defined in the same way as the equilibrium • If Qc < Kc, net reaction goes from left to
constant Kc except that the concentrations right
in Qc are not necessarily equilibrium values. • If Qc > Kc, net reaction goes from right to
For a general reaction: left.
aA+bB c C + d D (6.19) • If Qc = Kc, no net reaction occurs.
Qc = [C] [D] / [A] [B]
c d a b
(6.20)
Problem 6.7
Then,
The value of Kc for the reaction
If Qc > Kc, the reaction will proceed in the 2A B + C is 2 × 10–3. At a given time,
direction of reactants (reverse reaction). the composition of reaction mixture is
If Qc < Kc, the reaction will proceed in the [A] = [B] = [C] = 3 × 10–4 M. In which direction
the reaction will proceed?
direction of the products (forward reaction).

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Unit [Link] 182 9/12/2022 [Link] AM

 EQUILIBRIUM 183

Solution The total pressure at equilbrium was

For the reaction the reaction quotient Qc is found to be 9.15 bar. Calculate Kc, Kp and
given by, partial pressure at equilibrium.
Qc = [B][C]/ [A]2 Solution
as [A] = [B] = [C] = 3 × 10–4M
Qc = (3 ×10–4)(3 × 10 –4) / (3 ×10 –4)2 = 1 We know pV = nRT
as Qc > Kc so the reaction will proceed in the Total volume (V ) = 1 L
reverse direction.
Molecular mass of N2O4 = 92 g
6.6.3 Calculating Equilibrium Number of moles = 13.8g/92 g = 0.15
Concentrations of the gas (n)
In case of a problem in which we know the Gas constant (R) = 0.083 bar L mol–1K–1
initial concentrations but do not know any of Temperature (T ) = 400 K
the equilibrium concentrations, the following
three steps shall be followed: pV = nRT
Step 1. Write the balanced equation for the p × 1L = 0.15 mol × 0.083 bar L mol–1K–1
reaction. × 400 K
Step 2. Under the balanced equation, make p = 4.98 bar
a table that lists for each substance involved N2O4 2NO2
in the reaction: Initial pressure: 4.98 bar 0
(a) the initial concentration, At equilibrium: (4.98 – x) bar 2x bar
(b) the change in concentration on going to Hence,
equilibrium, and ptotal at equilibrium = pN + pNO
2O4 2
(c) the equilibrium concentration.
9.15 = (4.98 – x) + 2x
In constructing the table, define x as the
concentration (mol/L) of one of the substances 9.15 = 4.98 + x
that reacts on going to equilibrium, then use x = 9.15 – 4.98 = 4.17 bar
the stoichiometry of the reaction to determine Partial pressures at equilibrium are,
the concentrations of the other substances in
pN = 4.98 – 4.17 = 0.81bar
terms of x. 2O4
pNO = 2x = 2 × 4.17 = 8.34 bar
Step 3. Substitute the equilibrium 2

 
2
concentrations into the equilibrium equation K p = p NO2 / p N 2O4
for the reaction and solve for x. If you are
= (8.34)2/0.81 = 85.87
to solve a quadratic equation choose the
mathematical solution that makes chemical Kp = Kc(RT)∆n
sense. 85.87 = Kc(0.083 × 400)1
Step 4. Calculate the equilibrium Kc = 2.586 = 2.6
concentrations from the calculated value of x.
Step 5. Check your results by substituting Problem 6.9
them into the equilibrium equation. 3.00 mol of PCl5 kept in 1L closed reaction
vessel was allowed to attain equilibrium
at 380K. Calculate composition of the
Problem 6.8 mixture at equilibrium. Kc= 1.80
13.8g of N2O4 was placed in a 1L reaction Solution
vessel at 400K and allowed to attain PCl5 PCl3 + Cl2
equilibrium Initial
N 2O4 (g) 2NO2 (g) concentration: 3.0 0 0

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Unit [Link] 183 9/12/2022 [Link] AM

 184 chemistry

Taking antilog of both sides, we get,

Let x mol per litre of PCl5 be dissociated,
At equilibrium: K = e–∆G/RT (6.23)
(3-x) x x Hence, using the equation (6.23), the
Kc = [PCl3][Cl2]/[PCl5] reaction spontaneity can be interpreted in
terms of the value of ∆G .
1.8 = x2/ (3 – x)
• If ∆G  < 0, then –∆G /RT is positive,
x2 + 1.8x – 5.4 = 0
and e –∆DG /RT>1, making K >1, which
x = [–1.8 ± √(1.8)2 – 4(–5.4)]/2 implies a spontaneous reaction or the
x = [–1.8 ± √3.24 + 21.6]/2 reaction which proceeds in the forward
direction to such an extent that the
x = [–1.8 ± 4.98]/2
products are present predominantly.
x = [–1.8 + 4.98]/2 = 1.59
• If ∆G  > 0, then –∆G /RT is negative, and
[PCl5] = 3.0 – x = 3 –1.59 = 1.41 M
e –∆G </RT 1, that is , K < 1, which implies


[PCl3] = [Cl2] = x = 1.59 M a non-spontaneous reaction or a reaction

which proceeds in the forward direction
6.7 Relationship between to such a small degree that only a very
Equilibrium Constant K, minute quantity of product is formed.
Reaction Quotient Q and
Gibbs Energy G Problem 6.10
The value of Kc for a reaction does not depend The value of ∆G  for the phosphorylation of
on the rate of the reaction. However, as you glucose in glycolysis is 13.8 kJ/mol. Find
have studied in Unit 5, it is directly related the value of Kc at 298 K.
to the thermodynamics of the reaction and
in particular, to the change in Gibbs energy, Solution
∆G. If, ∆G  = 13.8 kJ/mol = 13.8 × 103J/mol
• ∆G is negative, then the reaction is Also, ∆G  = – RT lnKc
spontaneous and proceeds in the forward
direction. Hence, ln Kc = –13.8 × 103J/mol
(8.314 J mol –1K –1 × 298 K)
• ∆G is positive, then reaction is considered
non-spontaneous. Instead, as reverse ln Kc = – 5.569
reaction would have a negative ∆G, the Kc = e–5.569
products of the forward reaction shall be Kc = 3.81 × 10 –3
converted to the reactants.
Problem 6.11
• ∆G is 0, reaction has achieved equilibrium;
at this point, there is no longer any free Hydrolysis of sucrose gives,
energy left to drive the reaction. Sucrose + H2O Glucose + Fructose
A mathematical expression of this Equilibrium constant Kc for the reaction is
thermodynamic view of equilibrium can be 2 ×1013 at 300K. Calculate ∆G  at 300K.
described by the following equation:
Solution
∆G = ∆G + RT lnQ (6.21)
∆G  = – RT lnKc
where, G is standard Gibbs energy.

∆G  = – 8.314J mol–1K–1×
At equilibrium, when ∆G = 0 and Q = Kc, 300K × ln(2×1013)
the equation (6.21) becomes, ∆G  = – 7.64 ×104 J mol–1
∆G = ∆G + RT ln K = 0
6.8 FACTORS AFFECTING EQUILIBRIA
∆G = – RT lnK (6.22)
One of the principal goals of chemical
lnK = – ∆G / RT
synthesis is to maximise the conversion of the

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 EQUILIBRIUM 185

reactants to products while minimising the “When the concentration of any of the
expenditure of energy. This implies maximum reactants or products in a reaction at
yield of products at mild temperature and equilibrium is changed, the composition
pressure conditions. If it does not happen, of the equilibrium mixture changes so as
then the experimental conditions need to be to minimize the effect of concentration
adjusted. For example, in the Haber process changes”.
for the synthesis of ammonia from N2 and Let us take the reaction,
H2, the choice of experimental conditions is
of real economic importance. Annual world H2(g) + I2(g) 2HI(g)
production of ammonia is about hundred If H2 is added to the reaction mixture
million tones, primarily for use as fertilisers. at equilibrium, then the equilibrium of the
Equilibrium constant, Kc is independent reaction is disturbed. In order to restore it,
of initial concentrations. But if a system at the reaction proceeds in a direction wherein
equilibrium is subjected to a change in the H2 is consumed, i.e., more of H2 and I2 react
concentration of one or more of the reacting to form HI and finally the equilibrium shifts
substances, then the system is no longer at in right (forward) direction (Fig.6.8). This is in
equilibrium; and net reaction takes place in accordance with the Le Chatelier’s principle
some direction until the system returns to which implies that in case of addition of a
equilibrium once again. Similarly, a change reactant/product, a new equilibrium will
in temperature or pressure of the system may be set up in which the concentration of the
also alter the equilibrium. In order to decide reactant/product should be less than what it
what course the reaction adopts and make was after the addition but more than what it
a qualitative prediction about the effect of a was in the original mixture.
change in conditions on equilibrium we use
Le Chatelier’s principle. It states that a
change in any of the factors that determine
the equilibrium conditions of a system
will cause the system to change in such a
manner so as to reduce or to counteract
the effect of the change. This is applicable
to all physical and chemical equilibria.
We shall now be discussing factors which
can influence the equilibrium.
6.8.1 Effect of Concentration Change
In general, when equilibrium is disturbed
by the addition/removal of any reactant/
products, Le Chatelier’s principle predicts
that:
• The concentration stress of an added
reactant/product is relieved by net
reaction in the direction that consumes Fig. 6.8 Effect of addition of H 2 on change
of concentration for the reactants
the added substance. and products in the reaction,
• The concentration stress of a removed H2(g) + I2 (g) 2HI(g)
reactant/product is relieved by net
reaction in the direction that replenishes The same point can be explained in terms
the removed substance. of the reaction quotient, Qc,
or in other words, Qc = [HI]2/ [H2][I2]

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Unit [Link] 185 11/30/2022 [Link]

 186 chemistry

Addition of hydrogen at equilibrium concentration of [Fe(SCN)]2+ decreases, the

results in value of Qc being less than Kc . Thus, intensity of red colour decreases.
in order to attain equilibrium again reaction Addition of aq. HgCl2 also decreases red
moves in the forward direction. Similarly, colour because Hg2+ reacts with SCN– ions to
we can say that removal of a product also form stable complex ion [Hg(SCN)4]2–. Removal
boosts the forward reaction and increases of free SCN – (aq) shifts the equilibrium
the concentration of the products and this in equation (6.24) from right to left to
has great commercial application in cases replenish SCN – ions. Addition of potassium
of reactions, where the product is a gas or a thiocyanate on the other hand increases the
volatile substance. In case of manufacture of colour intensity of the solution as it shift the
ammonia, ammonia is liquified and removed equilibrium to right.
from the reaction mixture so that reaction
keeps moving in forward direction. Similarly, 6.8.2 Effect of Pressure Change
in the large scale production of CaO (used A pressure change obtained by changing the
as important building material) from CaCO3, volume can affect the yield of products in
constant removal of CO2 from the kiln drives case of a gaseous reaction where the total
the reaction to completion. It should be number of moles of gaseous reactants and
remembered that continuous removal of a total number of moles of gaseous products are
product maintains Qc at a value less than Kc different. In applying Le Chatelier’s principle
and reaction continues to move in the forward to a heterogeneous equilibrium the effect
direction. of pressure changes on solids and liquids
can be ignored because the volume (and
Effect of Concentration – An experiment concentration) of a solution/liquid is nearly
This can be demonstrated by the following independent of pressure.
reaction: Consider the reaction,
Fe3+(aq)+ SCN –(aq) [Fe(SCN)]2+(aq) (6.24)
CO(g) + 3H2(g) CH4(g) + H2O(g)
yellow colourless deep red
Here, 4 mol of gaseous reactants (CO + 3H2)
become 2 mol of gaseous products (CH4 +
H2O). Suppose equilibrium mixture (for above
(6.25) reaction) kept in a cylinder fitted with a piston
at constant temperature is compressed to
A reddish colour appears on adding two
one half of its original volume. Then, total
drops of 0.002 M potassium thiocynate solution
pressure will be doubled (according to
to 1 mL of 0.2 M iron(III) nitrate solution due
pV = constant). The partial pressure and
to the formation of [Fe(SCN)]2+. The intensity therefore, concentration of reactants and
of the red colour becomes constant on products have changed and the mixture is no
attaining equilibrium. This equilibrium can be longer at equilibrium. The direction in which
shifted in either forward or reverse directions the reaction goes to re-establish equilibrium
depending on our choice of adding a reactant can be predicted by applying the Le Chatelier’s
or a product. The equilibrium can be shifted principle. Since pressure has doubled,
in the opposite direction by adding reagents the equilibrium now shifts in the forward
that remove Fe3+ or SCN – ions. For example, direction, a direction in which the number
oxalic acid (H2C2O4), reacts with Fe3+ ions of moles of the gas or pressure decreases (we
to form the stable complex ion [Fe(C2O4)3]3–, know pressure is proportional to moles of the
thus decreasing the concentration of free gas). This can also be understood by using
Fe3+(aq). In accordance with the Le Chatelier’s reaction quotient, Qc. Let [CO], [H2], [CH4]
principle, the concentration stress of removed and [H2O] be the molar concentrations at
Fe3+ is relieved by dissociation of [Fe(SCN)]2+ equilibrium for methanation reaction. When
to replenish the Fe 3+ ions. Because the volume of the reaction mixture is halved, the

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Unit [Link] 186 9/12/2022 [Link] AM

 EQUILIBRIUM 187

partial pressure and the concentration are Production of ammonia according to the
doubled. We obtain the reaction quotient by reaction,
replacing each equilibrium concentration by N2(g) + 3H2(g) 2NH3(g);
double its value.
∆H= – 92.38 kJ mol–1
CH4 ( g ) H2O ( g )
Qc =  is an exothermic process. According to
CO ( g ) H2 ( g )
3
Le Chatelier’s principle, raising the
temperature shifts the equilibrium to left
As Qc < Kc , the reaction proceeds in the and decreases the equilibrium concentration
forward direction. of ammonia. In other words, low temperature
In reaction C(s) + CO2(g) 2CO(g), when is favourable for high yield of ammonia, but
practically very low temperatures slow down
pressure is increased, the reaction goes in the
the reaction and thus a catalyst is used.
reverse direction because the number of moles
of gas increases in the forward direction. Effect of Temperature – An experiment
Effect of temperature on equilibrium can
6.8.3 Effect of Inert Gas Addition
be demonstrated by taking NO2 gas (brown
If the volume is kept constant and an inert gas in colour) which dimerises into N 2O 4 gas
such as argon is added which does not take (colourless).
part in the reaction, the equilibrium remains
2NO2(g) N2O4(g); ∆H = –57.2 kJ mol–1
undisturbed. It is because the addition of
an inert gas at constant volume does not NO 2 gas prepared by addition of Cu
change the partial pressures or the molar turnings to conc. HNO3 is collected in two
concentrations of the substance involved in 5 mL test tubes (ensuring same intensity
the reaction. The reaction quotient changes of colour of gas in each tube) and stopper
only if the added gas is a reactant or product sealed with araldite. Three 250 mL beakers
involved in the reaction. 1, 2 and 3 containing freesing mixture, water
at room temperature and hot water (363K),
6.8.4 Effect of Temperature Change respectively, are taken (Fig. 6.9). Both the test
Whenever an equilibrium is disturbed by tubes are placed in beaker 2 for 8-10 minutes.
a change in the concentration, pressure or After this one is placed in beaker 1 and the
volume, the composition of the equilibrium other in beaker 3. The effect of temperature
mixture changes because the reaction on direction of reaction is depicted very well
quotient, Qc no longer equals the equilibrium in this experiment. At low temperatures in
constant, Kc. However, when a change in beaker 1, the forward reaction of formation of
temperature occurs, the value of equilibrium N2O4 is preferred, as reaction is exothermic,
constant, Kc is changed. and thus, intensity of brown colour due
to NO2 decreases. While in beaker 3, high
In general, the temperature dependence temperature favours the reverse reaction of
of the equilibrium constant depends on the
sign of ∆H for the reaction.
• The equilibrium constant for an exothermic
reaction (negative ∆H) decreases as the
temperature increases.
• The equilibrium constant for an
endothermic reaction (positive ∆H)
increases as the temperature increases.
Temperature changes affect the Fig. 6.9 Effect of temperature on equilibrium for
equilibrium constant and rates of reactions. the reaction, 2NO2 (g) N2O4 (g)

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 188 chemistry

formation of NO2 and thus, the brown colour Similarly, in manufacture of sulphuric
intensifies. acid by contact process,
Effect of temperature can also be seen in 2SO2(g) + O2(g) 2SO3(g); Kc = 1.7 × 1026
an endothermic reaction, though the value of K is suggestive of reaction
[Co(H2O) 6]3+ (aq) + 4Cl –(aq) [CoCl4]2–(aq) + going to completion, but practically the
6H2O(l) oxidation of SO2 to SO3 is very slow. Thus,
pink colourless blue platinum or divanadium penta-oxide (V2O5)
is used as catalyst to increase the rate of the
At room temperature, the equilibrium
mixture is blue due to [CoCl4]2–. When cooled reaction.
in a freesing mixture, the colour of the mixture Note: If a reaction has an exceedingly small
turns pink due to [Co(H2O)6]3+. K, a catalyst would be of little help.

6.8.5 Effect of a Catalyst 6.9 IONIC EQUILIBRIUM IN SOLUTION

A catalyst increases the rate of the chemical Under the effect of change of concentration
reaction by making available a new low energy on the direction of equilibrium, you have
pathway for the conversion of reactants to incidently come across with the following
products. It increases the rate of forward equilibrium which involves ions:
and reverse reactions that pass through the Fe3+(aq) + SCN–(aq) [Fe(SCN)]2+(aq)
same transition state and does not affect There are numerous equilibria that involve
equilibrium. Catalyst lowers the activation ions only. In the following sections we will
energy for the forward and reverse reactions study the equilibria involving ions. It is well
by exactly the same amount. Catalyst does known that the aqueous solution of sugar
not affect the equilibrium composition of does not conduct electricity. However, when
a reaction mixture. It does not appear in
common salt (sodium chloride) is added
the balanced chemical equation or in the
to water it conducts electricity. Also, the
equilibrium constant expression.
conductance of electricity increases with an
Let us consider the formation of NH3 increase in concentration of common salt.
from dinitrogen and dihydrogen which is Michael Faraday classified the substances
highly exothermic reaction and proceeds into two categories based on their ability
with decrease in total number of moles to conduct electricity. One category of
formed as compared to the reactants. substances conduct electricity in their
Equilibrium constant decreases with increase aqueous solutions and are called electrolytes
in temperature. At low temperature rate while the other do not and are thus, referred to
decreases and it takes long time to reach at as non-electrolytes. Faraday further classified
equilibrium, whereas high temperatures give electrolytes into strong and weak electrolytes.
satisfactory rates but poor yields. Strong electrolytes on dissolution in water
German chemist, Fritz Haber discovered are ionized almost completely, while the weak
that a catalyst consisting of iron catalyse electrolytes are only partially dissociated.
the reaction to occur at a satisfactory rate For example, an aqueous solution of
at temperatures, where the equilibrium sodium chloride is comprised entirely of
concentration of NH3 is reasonably favourable. sodium ions and chloride ions, while that
Since the number of moles formed in the of acetic acid mainly contains unionized
reaction is less than those of reactants, the acetic acid molecules and only some acetate
yield of NH3 can be improved by increasing ions and hydronium ions. This is because
the pressure. there is almost 100% ionization in case
Optimum conditions of temperature of sodium chloride as compared to less
and pressure for the synthesis of NH3 using than 5% ionization of acetic acid which is
catalyst are around 500 °C and 200 atm. a weak electrolyte. It should be noted

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Unit [Link] 188 11/2/2022 [Link] PM

 EQUILIBRIUM 189

that in weak electrolytes, equilibrium is exists in solid state as a cluster of positively

established between ions and the unionized charged sodium ions and negatively charged
molecules. This type of equilibrium involving chloride ions which are held together due to
ions in aqueous solution is called ionic electrostatic interactions between oppositely
equilibrium. Acids, bases and salts come charged species (Fig.6.10). The electrostatic
under the category of electrolytes and may act forces between two charges are inversely
as either strong or weak electrolytes. proportional to dielectric constant of the
medium. Water, a universal solvent, possesses
6.10 ACIDS, BASES AND SALTS a very high dielectric constant of 80. Thus,
Acids, bases and salts find widespread when sodium chloride is dissolved in water,
occurrence in nature. Hydrochloric acid the electrostatic interactions are reduced by
present in the gastric juice is secreted by the a factor of 80 and this facilitates the ions to
lining of our stomach in a significant amount move freely in the solution. Also, they are
of 1.2-1.5 L/day and is essential for digestive well-separated due to hydration with water
processes. Acetic acid is known to be the main molecules.
constituent of vinegar. Lemon and orange
juices contain citric and ascorbic acids, and
tartaric acid is found in tamarind paste. As
most of the acids taste sour, the word “acid”
has been derived from a latin word “acidus”
meaning sour. Acids are known to turn blue
litmus paper into red and liberate dihydrogen
on reacting with some metals. Similarly, bases
are known to turn red litmus paper blue, taste
bitter and feel soapy. A common example
of a base is washing soda used for washing
purposes. When acids and bases are mixed
in the right proportion they react with each
Fig.6.10 Dissolution of sodium chloride in water.
other to give salts. Some commonly known
Na+ and Cl – ions are stablised by their
examples of salts are sodium chloride, barium hydration with polar water molecules.
sulphate, sodium nitrate. Sodium chloride
(common salt) is an important component of Comparing, the ionization of hydrochloric
our diet and is formed by reaction between acid with that of acetic acid in water we find
hydrochloric acid and sodium hydroxide. It that though both of them are polar covalent

Faraday was born near London into a family of very limited means. At the age of
14 he was an apprentice to a kind bookbinder who allowed Faraday to read the
books he was binding. Through a fortunate chance he became laboratory assistant
to Davy, and during 1813-4, Faraday accompanied him to the Continent. During
this trip he gained much from the experience of coming into contact with many of the
leading scientists of the time. In 1825, he succeeded Davy as Director of the Royal
Institution laboratories, and in 1833 he also became the first Fullerian Professor of
Chemistry. Faraday’s first important work was on analytical chemistry. After 1821
Michael Faraday
much of his work was on electricity and magnetism and different electromagnetic
(1791–1867)
phenomena. His ideas have led to the establishment of modern field theory.
He discovered his two laws of electrolysis in 1834. Faraday was a very modest and kind hearted
person. He declined all honours and avoided scientific controversies. He preferred to work alone and
never had any assistant. He disseminated science in a variety of ways including his Friday evening
discourses, which he founded at the Royal Institution. He has been very famous for his Christmas
lecture on the ‘Chemical History of a Candle’. He published nearly 450 scientific papers.

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 190 chemistry

molecules, former is completely ionized into

its constituent ions, while the latter is only Hydronium and Hydroxyl Ions
partially ionized (< 5%). The extent to which Hydrogen ion by itself is a bare proton with very
ionization occurs depends upon the strength small size (~10–15 m radius) and intense electric
of the bond and the extent of solvation field, binds itself with the water molecule at
of ions produced. The terms dissociation one of the two available lone pairs on it giving
and ionization have earlier been used with H3O+. This species has been detected in many
different meaning. Dissociation refers to the compounds (e.g., H3O+Cl–) in the solid state. In
process of separation of ions in water already aqueous solution the hydronium ion is further
existing as such in the solid state of the solute, hydrated to give species like H5O2+, H7O3+ and
as in sodium chloride. On the other hand, H9O4+. Similarly the hydroxyl ion is hydrated
to give several ionic species like H3O2–, H5O3–
ionization corresponds to a process in which
and H7O4– etc.
a neutral molecule splits into charged ions in
the solution. Here, we shall not distinguish
between the two and use the two terms
interchangeably.

6.10.1 Arrhenius Concept of Acids and

Bases
According to Arrhenius theory, acids are H9O4+
substances that dissociates in water to
give hydrogen ions H +(aq) and bases are 6.10.2 The Brönsted-Lowry Acids and
substances that produce hydroxyl ions Bases
OH –(aq). The ionization of an acid HX (aq) can The Danish chemist, Johannes Brönsted and
be represented by the following equations: the English chemist, Thomas M. Lowry gave
HX (aq) → H+(aq) + X– (aq) a more general definition of acids and bases.
or According to Brönsted-Lowry theory, acid
HX(aq) + H2O(l) → H3O+(aq) + X –(aq) is a substance that is capable of donating a
hydrogen ion H+ and bases are substances
A bare proton, H+ is very reactive and
capable of accepting a hydrogen ion, H+. In
cannot exist freely in aqueous solutions.
short, acids are proton donors and bases are
Thus, it bonds to the oxygen atom of a solvent
proton acceptors.
water molecule to give trigonal pyramidal
hydronium ion, H3O+ {[H (H2O)]+} (see box). In Consider the example of dissolution of NH3
this chapter we shall use H+(aq) and H3O+(aq) in H2O represented by the following equation:
interchangeably to mean the same i.e., a
hydrated proton.
Similarly, a base molecule like MOH
ionizes in aqueous solution according to the
equation:
MOH(aq) → M+(aq) + OH–(aq)
The hydroxyl ion also exists in the hydrated
form in the aqueous solution. Arrhenius
concept of acid and base, however, suffers The basic solution is formed due to the
from the limitation of being applicable only to presence of hydroxyl ions. In this reaction,
aqueous solutions and also, does not account water molecule acts as proton donor and
for the basicity of substances like, ammonia ammonia molecule acts as proton acceptor
which do not possess a hydroxyl group. and are thus, called Lowry-Brönsted acid and

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 EQUILIBRIUM 191

Arrhenius was born near Uppsala, Sweden. He presented his thesis, on the
conductivities of electrolyte solutions, to the University of Uppsala in 1884. For the
next five years he travelled extensively and visited a number of research centers
in Europe. In 1895 he was appointed professor of physics at the newly formed
University of Stockholm, serving its rector from 1897 to 1902. From 1905 until his
death he was Director of physical chemistry at the Nobel Institute in Stockholm. He
continued to work for many years on electrolytic solutions. In 1899 he discussed
the temperature dependence of reaction rates on the basis of an equation, now
usually known as Arrhenius equation.
He worked in a variety of fields, and made important contributions to
Svante Arrhenius
immunochemistry, cosmology, the origin of life, and the causes of ice age. He was
(1859-1927)
the first to discuss the ‘green house effect’ calling by that name. He received Nobel
Prize in Chemistry in 1903 for his theory of electrolytic dissociation and its use in
the development of chemistry.

base, respectively. In the reverse reaction, in case of ammonia it acts as an acid by

H+ is transferred from NH4+ to OH–. In this donating a proton.
case, NH 4+ acts as a Bronsted acid while
Problem 6.12
OH– acted as a Brönsted base. The acid-base
pair that differs only by one proton is called What will be the conjugate bases for the
a conjugate acid-base pair. Therefore, OH – following Brönsted acids: HF, H2SO4 and
HCO3– ?
is called the conjugate base of an acid H2O
and NH4+ is called conjugate acid of the base Solution
NH3. If Brönsted acid is a strong acid then The conjugate bases should have one
its conjugate base is a weak base and vice- proton less in each case and therefore the
versa. It may be noted that conjugate acid corresponding conjugate bases are: F –,
has one extra proton and each conjugate base HSO4– and CO32– respectively.
has one less proton.
Problem 6.13
Consider the example of ionization of
Write the conjugate acids for the following
hydrochloric acid in water. HCl(aq) acts as Brönsted bases: NH2–, NH3 and HCOO–.
an acid by donating a proton to H2O molecule
which acts as a base. Solution
The conjugate acid should have one extra
proton in each case and therefore the
corresponding conjugate acids are: NH3,
NH4+ and HCOOH respectively.
Problem 6.14
The species: H2O, HCO3–, HSO4– and NH3 can
act both as Bronsted acids and bases. For
each case give the corresponding conjugate
It can be seen in the above equation, that acid and conjugate base.
water acts as a base because it accepts the
Solution
proton. The species H3O+ is produced when
water accepts a proton from HCl. Therefore, The answer is given in the following Table:
Cl – is a conjugate base of HCl and HCl is the Species Conjugate Conjugate
conjugate acid of base Cl –. Similarly, H2O is acid base
a conjugate base of an acid H3O+ and H3O+ is
H2O H3O+ OH –
a conjugate acid of base H2O.
HCO3– H2CO3 CO32–
It is interesting to observe the dual role
HSO4– H2SO4 SO42–
of water as an acid and a base. In case of
reaction with HCl water acts as a base while NH3 NH4+ NH2–

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 192 chemistry

6.10.3 Lewis Acids and Bases (HClO4), hydrochloric acid (HCl), hydrobromic
G.N. Lewis in 1923 defined an acid as a acid (HBr), hyrdoiodic acid (HI), nitric acid
species which accepts electron pair and base (HNO3) and sulphuric acid (H2SO4) are termed
which donates an electron pair. As far as bases strong because they are almost completely
are concerned, there is not much difference dissociated into their constituent ions in an
between Brönsted-Lowry and Lewis concepts, aqueous medium, thereby acting as proton
as the base provides a lone pair in both the (H +) donors. Similarly, strong bases like
cases. However, in Lewis concept many lithium hydroxide (LiOH), sodium hydroxide
acids do not have proton. A typical example (NaOH), potassium hydroxide (KOH), caesium
is reaction of electron deficient species BF3 hydroxide (CsOH) and barium hydroxide
with NH3. Ba(OH)2 are almost completely dissociated
into ions in an aqueous medium giving
BF3 does not have a proton but still acts
hydroxyl ions, OH–. According to Arrhenius
as an acid and reacts with NH3 by accepting
concept they are strong acids and bases as
its lone pair of electrons. The reaction can be
they are able to completely dissociate and
represented by,
produce H3O+ and OH– ions respectively in
BF3 + :NH3 → BF3:NH3 the medium. Alternatively, the strength of an
Electron deficient species like AlCl3, Co3+, acid or base may also be gauged in terms of
Mg2+, etc. can act as Lewis acids while species Brönsted-Lowry concept of acids and bases,
like H2O, NH3, OH– etc. which can donate a wherein a strong acid means a good proton
pair of electrons, can act as Lewis bases. donor and a strong base implies a good proton
acceptor. Consider, the acid-base dissociation
Problem 6.15 equilibrium of a weak acid HA,
Classify the following species into Lewis HA(aq) + H2O(l)   H3O+(aq) + A–(aq)
acids and Lewis bases and show how these conjugate conjugate
act as such: acid base acid base
(a) HO – (b) F – (c) H+ (d) BCl3 In section 6.10.2 we saw that acid (or
Solution base) dissociation equilibrium is dynamic
involving a transfer of proton in forward and
(a) Hydroxyl ion is a Lewis base as it can reverse directions. Now, the question arises
donate an electron lone pair (:OH– ). that if the equilibrium is dynamic then with
(b) Flouride ion acts as a Lewis base passage of time which direction is favoured?
as it can donate any one of its four What is the driving force behind it? In order
electron lone pairs. to answer these questions we shall deal
(c) A proton is a Lewis acid as it can into the issue of comparing the strengths
accept a lone pair of electrons from of the two acids (or bases) involved in the
bases like hydroxyl ion and fluoride dissociation equilibrium. Consider the two
ion. acids HA and H 3O + present in the above
(d) BCl3 acts as a Lewis acid as it can mentioned acid-dissociation equilibrium.
accept a lone pair of electrons from We have to see which amongst them is a
species like ammonia or amine stronger proton donor. Whichever exceeds
molecules. in its tendency of donating a proton over the
other shall be termed as the stronger acid
6.11 IONIZATION OF ACIDS AND BASES and the equilibrium will shift in the direction
of weaker acid. Say, if HA is a stronger acid
Arrhenius concept of acids and bases
than H3O+, then HA will donate protons and
becomes useful in case of ionization of acids
not H3O+, and the solution will mainly contain
and bases as mostly ionizations in chemical
A– and H3O+ ions. The equilibrium moves in
and biological systems occur in aqueous
the direction of formation of weaker acid
medium. Strong acids like perchloric acid

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 EQUILIBRIUM 193

and weaker base because the stronger acid H2O(l) + H2O(l) H3O+(aq) + OH–(aq)
donates a proton to the stronger base. acid base conjugate conjugate
It follows that as a strong acid dissociates acid base
completely in water, the resulting base formed The dissociation constant is represented by,
would be very weak i.e., strong acids have K = [H3O+] [OH–] / [H2O] (6.26)
very weak conjugate bases. Strong acids
like perchloric acid (HClO4), hydrochloric acid The concentration of water is omitted from
(HCl), hydrobromic acid (HBr), hydroiodic acid the denominator as water is a pure liquid and
(HI), nitric acid (HNO3) and sulphuric acid its concentration remains constant. [H2O] is
(H2SO4) will give conjugate base ions ClO4–, Cl, incorporated within the equilibrium constant
Br–, I–, NO3– and HSO4– , which are much weaker to give a new constant, Kw, which is called the
bases than H2O. Similarly a very strong base ionic product of water.
would give a very weak conjugate acid. On the Kw = [H+][OH–] (6.27)
other hand, a weak acid say HA is only partially
The concentration of H has been found
+
dissociated in aqueous medium and thus, the
out experimentally as 1.0 × 10–7 M at 298 K.
solution mainly contains undissociated HA
And, as dissociation of water produces equal
molecules. Typical weak acids are nitrous
number of H+ and OH– ions, the concentration
acid (HNO2), hydrofluoric acid (HF) and acetic
of hydroxyl ions, [OH–] = [H+] = 1.0 × 10–7 M.
acid (CH3COOH). It should be noted that the
weak acids have very strong conjugate bases. Thus, the value of Kw at 298K,
For example, NH2–, O 2– and H – are very good Kw = [H3O+][OH–] = (1 × 10–7)2 = 1 × 10–14 M2
proton acceptors and thus, much stronger (6.28)
bases than H2O.
The value of Kw is temperature dependent
Certain water soluble organic compounds as it is an equilibrium constant.
like phenolphthalein and bromothymol blue
The density of pure water is 1000 g / L
behave as weak acids and exhibit different
and its molar mass is 18.0 g /mol. From this
colours in their acid (HIn) and conjugate base
the molarity of pure water can be given as,
(In– ) forms.
[H2O] = (1000 g /L)(1 mol/18.0 g) = 55.55 M.
HIn(aq) + H2O(l) H3O+(aq) + In–(aq)
Therefore, the ratio of dissociated water to
acid conjugate conjugate
that of undissociated water can be given as:
indicator acid base
10 –7 / (55.55) = 1.8 × 10–9 or ~ 2 in 10–9 (thus,
colour A colour B equilibrium lies mainly towards undissociated
Such compounds are useful as indicators water)
in acid-base titrations, and finding out H+ ion
concentration. We can distinguish acidic, neutral and
basic aqueous solutions by the relative values
6.11.1 The Ionization Constant of Water of the H3O+ and OH– concentrations:
and its Ionic Product
Acidic: [H3O+] > [OH– ]
Some substances like water are unique in
their ability of acting both as an acid and a Neutral: [H3O+] = [OH– ]
base. We have seen this in case of water in Basic : [H3O+] < [OH–]
section 6.10.2. In presence of an acid, HA it
accepts a proton and acts as the base while 6.11.2 The pH Scale
in the presence of a base, B– it acts as an Hydronium ion concentration in molarity is
acid by donating a proton. In pure water, one more conveniently expressed on a logarithmic
H2O molecule donates proton and acts as an scale known as the pH scale. The pH of a
acid and another water molecules accepts a solution is defined as the negative logarithm
proton and acts as a base at the same time.
The following equilibrium exists:
to base 10 of the activity a H   of hydrogen

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 194 chemistry

ion. In dilute solutions (< 0.01 M), activity when the hydrogen ion concentration, [H+]
of hydrogen ion (H+) is equal in magnitude changes by a factor of 100, the value of pH
to molarity represented by [H+]. It should changes by 2 units. Now you can realise why
be noted that activity has no units and is the change in pH with temperature is often
defined as: ignored.
= [H+] / mol L–1 Measurement of pH of a solution is very
From the definition of pH, the following essential as its value should be known
when dealing with biological and cosmetic
can be written,
applications. The pH of a solution can be
pH = – log aH+ = – log {[H+] / mol L–1} found roughly with the help of pH paper that
Thus, an acidic solution of HCl (10–2 M) has different colour in solutions of different
will have a pH = 2. Similarly, a basic solution pH. Now-a-days pH paper is available with
of NaOH having [OH–] =10–4 M and [H3O+] = four strips on it. The different strips have
10–10 M will have a pH = 10. At 25 °C, pure different colours (Fig. 6.11) at the same pH.
water has a concentration of hydrogen ions, The pH in the range of 1-14 can be determined
[H + ] = 10–7 M. Hence, the pH of pure water is with an accuracy of ~0.5 using pH paper.
given as:
pH = –log(10–7) = 7
Acidic solutions possess a concentration
of hydrogen ions, [H + ] > 10–7 M, while basic
solutions possess a concentration of hydrogen
ions, [H+] < 10–7 M. thus, we can summarise
that
Fig.6.11 pH-paper with four strips that may have
Acidic solution has pH < 7 different colours at the same pH
Basic solution has pH > 7
Neutral solution has pH = 7 For greater accuracy pH meters are used.
pH meter is a device that measures the
Now again, consider the equation (6.28)
pH-dependent electrical potential of the test
at 298 K
solution within 0.001 precision. pH meters
Kw = [H3O+] [OH–] = 10–14
of the size of a writing pen are now available
Taking negative logarithm on both sides in the market. The pH of some very common
of equation, we obtain substances are given in Table 6.5 (page 195).
–log Kw = – log {[H3O+] [OH–]}
Problem 6.16
= – log [H3O+] – log [OH–]
The concentration of hydrogen ion in a
= – log 10 –14
sample of soft drink is 3.8 × 10–3M. what
pKw = pH + pOH = 14 (6.29) is its pH ?
Note that although K w may change
with temperature the variations in pH with Solution
temperature are so small that we often pH = – log[3.8 × 10–3]
ignore it. = – {log[3.8] + log[10–3]}
pK w is a very important quantity for = – {(0.58) + (– 3.0)} = – { – 2.42} = 2.42
aqueous solutions and controls the relative Therefore, the pH of the soft drink is 2.42
concentrations of hydrogen and hydroxyl and it can be inferred that it is acidic.
ions as their product is a constant. It should
Problem 6.17
be noted that as the pH scale is logarithmic,
a change in pH by just one unit also means Calculate pH of a 1.0 × 10 –8 M solution of
change in [H+] by a factor of 10. Similarly, HCl.

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 EQUILIBRIUM 195

Table 6.5 The pH of Some Common Substances

Name of the Fluid pH Name of the Fluid pH

Saturated solution of NaOH ~15 Black Coffee 5.0

0.1 M NaOH solution 13 Tomato juice ~4.2
Lime water 10.5 Soft drinks and vinegar ~3.0
Milk of magnesia 10 Lemon juice ~2.2
Egg white, sea water 7.8 Gastric juice ~1.2
Human blood 7.4 1M HCl solution ~0
Milk 6.8 Concentrated HCl ~–1.0
Human Saliva 6.4

Solution equilibrium constant for the above discussed

acid-dissociation equilibrium:
2H2O (l) H3O+ (aq) + OH–(aq) Ka = c2α2 / c(1-α) = cα2 / 1-α
Kw = [OH ][H3O+]
–
Ka is called the dissociation or ionization
= 10–14 constant of acid HX. It can be represented
Let, x = [OH –] = [H 3O +] from H 2O. The alternatively in terms of molar concentration
H3O+ concentration is generated (i) from as follows,
the ionization of HCl dissolved i.e.,
Ka = [H+][X –] / [HX] (6.30)
HCl(aq) + H2O(l) H3O+ (aq) + Cl –(aq),
At a given temperature T, K a is a
and (ii) from ionization of H2O. In these very measure of the strength of the acid HX i.e.,
dilute solutions, both sources of H3O+ must larger the value of Ka, the stronger is the
be considered:
acid. Ka is a dimensionless quantity with
[H3O+] = 10–8 + x the understanding that the standard state
Kw = (10–8 + x)(x) = 10–14 concentration of all species is 1M.
or x2 + 10–8 x – 10–14 = 0 The values of the ionization constants
[OH – ] = x = 9.5 × 10–8 of some selected weak acids are given in
So, pOH = 7.02 and pH = 6.98 Table 6.6.
Table 6.6 The Ionization Constants of Some
6.11.3 Ionization Constants of Weak Acids Selected Weak Acids (at 298K)
Consider a weak acid HX that is partially Acid Ionization Constant,
ionized in the aqueous solution. The Ka
equilibrium can be expressed by:
Hydrofluoric Acid (HF) 3.5 × 10–4
HX(aq) + H2O(l) H3O+(aq) + X –(aq)
Nitrous Acid (HNO2) 4.5 × 10–4
Initial
Formic Acid (HCOOH) 1.8 × 10–4
concentration (M)
c 0 0 Niacin (C5H4NCOOH) 1.5 × 10–5
Let α be the extent of ionization Acetic Acid (CH3COOH) 1.74 × 10–5
Change (M) Benzoic Acid (C6H5COOH) 6.5 × 10–5
-cα +cα +cα Hypochlorous Acid (HCIO) 3.0 × 10–8
Equilibrium concentration (M) Hydrocyanic Acid (HCN) 4.9 × 10–10
c-cα cα cα Phenol (C6H5OH) 1.3 × 10–10
Here, c = initial concentration of the
undissociated acid, HX at time, t = 0. α = The pH scale for the hydrogen ion
extent up to which HX is ionized into ions. concentration has been so useful that besides
Using these notations, we can derive the pKw, it has been extended to other species and

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 196 chemistry

quantities. Thus, we have:

Solution
pKa = –log (Ka) (6.31)
The following proton transfer reactions are
Knowing the ionization constant, K a possible:
of an acid and its initial concentration, c, 1) HF + H2O H3O+ + F –
it is possible to calculate the equilibrium
Ka = 3.2 × 10–4
concentration of all species and also the
degree of ionization of the acid and the pH of 2) H2O + H2O H3O+ + OH –
the solution. Kw = 1.0 × 10–14
A general step-wise approach can be As Ka >> Kw, [1] is the principle reaction.
adopted to evaluate the pH of the weak HF + H2O H3O+ + F–
electrolyte as follows: Initial
Step 1. The species present before concentration (M)
dissociation are identified as Brönsted-Lowry 0.02 0 0
acids/bases. Change (M)
Step 2. Balanced equations for all possible –0.02α +0.02α +0.02α
reactions i.e., with a species acting both as
Equilibrium
acid as well as base are written.
Step 3. The reaction with the higher Ka is concentration (M)
identified as the primary reaction whilst the 0.02 – 0.02 α 0.02 α 0.02α
other is a subsidiary reaction. Substituting equilibrium concentrations
Step 4. Enlist in a tabular form the following in the equilibrium reaction for principal
values for each of the species in the primary reaction gives:
reaction Ka = (0.02α)2 / (0.02 – 0.02α)
(a) Initial concentration, c. = 0.02 α2 / (1 –α) = 3.2 × 10–4
(b) Change in concentration on proceeding We obtain the following quadratic equation:
to equilibrium in terms of α, degree of α2 + 1.6 × 10–2α – 1.6 × 10–2 = 0
ionization. The quadratic equation in α can be solved
(c) Equilibrium concentration. and the two values of the roots are:
Step 5. Substitute equilibrium concentrations α = + 0.12 and – 0.12
into equilibrium constant equation for The negative root is not acceptable and
principal reaction and solve for α. hence,
Step 6. Calculate the concentration of species α = 0.12
in principal reaction. This means that the degree of ionization,
Step 7. Calculate pH = – log[H3O+] α = 0.12, then equilibrium concentrations
of other species viz., HF, F – and H3O+ are
The above mentioned methodology has given by:
been elucidated in the following examples.
[H3O+] = [F –] = cα = 0.02 × 0.12
= 2.4 × 10–3 M
Problem 6.18 [HF] = c(1 – α) = 0.02 (1 – 0.12)
The ionization constant of HF is
3.2 × 10 –4 . Calculate the degree of = 17.6 × 10-3 M
dissociation of HF in its 0.02 M solution. pH = – log[H+] = –log(2.4 × 10–3) = 2.62
Calculate the concentration of all species Problem 6.19
present (H3O+, F – and HF) in the solution
and its pH. The pH of 0.1M monobasic acid is 4.50.
Calculate the concentration of species H+, A–

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 EQUILIBRIUM 197

and HA at equilibrium. Also, determine the Percent dissociation

value of Ka and pKa of the monobasic acid. = {[HOCl]dissociated / [HOCl]initial }× 100
Solution = 1.41 × 10–3 × 102/ 0.08 = 1.76 %.
pH = –log(1.41 × 10–3) = 2.85.
pH = – log [H+]
Therefore, [H+] = 10 –pH
= 10 –4.50 6.11.4 Ionization of Weak Bases
= 3.16 × 10 –5 The ionization of base MOH can be represented
by equation:
[H+] = [A–] = 3.16 × 10–5
MOH(aq) M+(aq) + OH–(aq)
Thus, Ka = [H+][A-] / [HA]
In a weak base there is partial ionization
[HA]eqlbm = 0.1 – (3.16 × 10-5)  0.1 of MOH into M+ and OH–, the case is similar
Ka = (3.16 × 10–5)2 / 0.1 = 1.0 × 10–8 to that of acid-dissociation equilibrium. The
equilibrium constant for base ionization
pKa = – log(10–8) = 8 is called base ionization constant and is
Alternatively, “Percent dissociation” is represented by Kb. It can be expressed in
another useful method for measure of terms of concentration in molarity of various
strength of a weak acid and is given as: species in equilibrium by the following
Percent dissociation equation:
= [HA]dissociated/[HA]initial × 100% (6.32) Kb = [M+][OH–] / [MOH] (6.33)
Alternatively, if c = initial concentration
Problem 6.20 of base and α = degree of ionization of base
Calculate the pH of 0.08M solution of i.e. the extent to which the base ionizes.
hypochlorous acid, HOCl. The ionization When equilibrium is reached, the equilibrium
constant of the acid is 2.5 × 10 –5. Determine constant can be written as:
the percent dissociation of HOCl. Kb = (cα)2 / c (1-α) = cα2 / (1-α)
Solution The values of the ionization constants of
HOCl(aq) + H2O (l) H3O+(aq) + ClO–(aq) some selected weak bases, Kb are given in
Table 6.7.
Initial concentration (M)
0.08 0 0 Table 6.7 The Values of the Ionization
Constant of Some Weak Bases at
Change to reach 298 K
equilibrium concentration Base Kb
(M)
Dimethylamine, (CH3)2NH 5.4 × 10–4
– x + x +x
Triethylamine, (C2H5)3N 6.45 × 10–5
equilibrium concentartion (M)
Ammonia, NH3 or NH4OH 1.77 × 10–5
0.08 – x x x
Quinine, (A plant product) 1.10 × 10–6
Ka = {[H3O ][ClO ] / [HOCl]}
+ –
Pyridine, C5H5N 1.77 × 10–9
= x / (0.08 –x)
2
Aniline, C6H5NH2 4.27 × 10–10
As x << 0.08, therefore 0.08 – x  0.08 Urea, CO (NH2)2 1.3 × 10–14
x2 / 0.08 = 2.5 × 10–5 Many organic compounds like amines
x2 = 2.0 × 10–6, thus, x = 1.41 × 10–3 are weak bases. Amines are derivatives of
[H+] = 1.41 × 10–3 M. ammonia in which one or more hydrogen
Therefore, atoms are replaced by another group. For
example, methylamine, codeine, quinine and

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 198 chemistry

nicotine all behave as very weak bases due to

Kb = 10–4.75 = 1.77 × 10–5 M
their very small Kb. Ammonia produces OH– in
aqueous solution: NH3 + H2O NH4+ + OH–
NH3(aq) + H2O(l) NH4+(aq) + OH–(aq) Initial concentration (M)
0.10 0.20 0
The pH scale for the hydrogen ion
concentration has been extended to get: Change to reach
pKb = –log (Kb) (6.34) equilibrium (M)
–x +x +x
At equilibrium (M)
Problem 6.21 0.10 – x 0.20 + x x
The pH of 0.004M hydrazine solution is 9.7. Kb = [NH4 ][OH ] / [NH3]
+ –
Calculate its ionization constant Kb and pKb.
= (0.20 + x)(x) / (0.1 – x) = 1.77 × 10–5
Solution
As Kb is small, we can neglect x in comparison
NH2NH2 + H2O NH2NH3+ + OH– to 0.1M and 0.2M. Thus,
From the pH we can calculate the hydrogen [OH–] = x = 0.88 × 10–5
ion concentration. Knowing hydrogen ion Therefore, [H+] = 1.12 × 10–9
concentration and the ionic product of
pH = – log[H+] = 8.95.
water we can calculate the concentration
of hydroxyl ions. Thus we have:
6.11.5 Relation between Ka and Kb
[H+] = antilog (–pH) As seen earlier in this chapter, Ka and Kb
= antilog (–9.7) = 1.67 ×10–10 represent the strength of an acid and a base,
[OH–] = Kw / [H+] = 1 × 10–14 / 1.67 × 10–10 respectively. In case of a conjugate acid-base
= 5.98 × 10–5 pair, they are related in a simple manner so
that if one is known, the other can be deduced.
The concentration of the corresponding
Considering the example of NH4+ and NH3
hydrazinium ion is also the same as that
of hydroxyl ion. The concentration of both we see,
these ions is very small so the concentration NH4+(aq) + H2O(l) H3O+(aq) + NH3(aq)
of the undissociated base can be taken Ka = [H3O+][ NH3] / [NH4+] = 5.6 × 10–10
equal to 0.004M.
NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)
Thus,
Kb =[ NH4 ][ OH ] / NH3 = 1.8 × 10–5
+ –

Kb = [NH2NH3+][OH–] / [NH2NH2]
Net: 2 H2O(l) H3O+(aq) + OH –(aq)
= (5.98 × 10–5)2 / 0.004 = 8.96 × 10–7
Kw = [H3O+][ OH– ] = 1.0 × 10–14 M
pKb = –logKb = –log(8.96 × 10–7) = 6.04.
Where, Ka represents the strength of NH4+
Problem 6.22 as an acid and Kb represents the strength of
Calculate the pH of the solution in which NH3 as a base.
0.2M NH4Cl and 0.1M NH3 are present. The It can be seen from the net reaction that
pKb of ammonia solution is 4.75. the equilibrium constant is equal to the
product of equilibrium constants Ka and Kb
Solution
for the reactions added. Thus,
NH3 + H2O NH4+ + OH– Ka × K b = {[H3O+][ NH3] / [NH4+ ]} × {[NH4+]
The ionization constant of NH3, [OH–] / [NH3]}
Kb = antilog (–pKb) i.e. = [H3O+][OH–] = Kw
= (5.6 ×10–10) × (1.8 × 10–5) = 1.0 × 10–14 M

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 EQUILIBRIUM 199

This can be extended to make a

NH3 + H2O NH4+ + OH–
generalisation. The equilibrium constant
for a net reaction obtained after adding We use equation (6.33) to calculate
hydroxyl ion concentration,
two (or more) reactions equals the product
of the equilibrium constants for individual [OH–] = c α = 0.05 α
reactions: Kb = 0.05 α2 / (1 – α)
K NET = K1 × K2 × …… (6.35) The value of α is small, therefore the
quadratic equation can be simplified by
Similarly, in case of a conjugate acid-base neglecting α in comparison to 1 in the
pair, denominator on right hand side of the
Ka × Kb = Kw (6.36) equation,
Knowing one, the other can be obtained. Thus,
It should be noted that a strong acid will have Kb = c α2 or α = √ (1.77 × 10–5 / 0.05)
a weak conjugate base and vice-versa. = 0.018.
Alternatively, the above expression [OH ] = c α = 0.05 × 0.018 = 9.4 × 10–4M.
–

K w = K a × K b , can also be obtained by

considering the base-dissociation equilibrium [H+] = Kw / [OH–] = 10–14 / (9.4 × 10–4)
reaction: = 1.06 × 10–11
B(aq) + H2O(l) BH+(aq) + OH–(aq) pH = –log(1.06 × 10–11) = 10.97.
K b = [BH+][OH–] / [B] Now, using the relation for conjugate
As the concentration of water remains acid-base pair,
constant it has been omitted from the Ka × Kb = Kw
denominator and incorporated within the
using the value of K b of NH 3 from
dissociation constant. Then multiplying and
Table 6.7.
dividing the above expression by [H+], we get:
Kb = [BH+][OH –][H+] / [B][H+] We can determine the concentration of
conjugate acid NH4+
={[ OH–][H+]}{[BH+] / [B][H+]}
Ka = Kw / Kb = 10–14 / 1.77 × 10–5
= Kw / Ka
or Ka × Kb = Kw = 5.64 × 10–10.
It may be noted that if we take negative
logarithm of both sides of the equation, then 6.11.6 Di- and Polybasic Acids and Di-
pK values of the conjugate acid and base are and Polyacidic Bases
related to each other by the equation: Some of the acids like oxalic acid, sulphuric
pKa + pKb = pKw = 14 (at 298K) acid and phosphoric acids have more than
one ionizable proton per molecule of the
Problem 6.23 acid. Such acids are known as polybasic or
polyprotic acids.
Determine the degree of ionization and pH of
The ionization reactions for example for
a 0.05M of ammonia solution. The ionization
a dibasic acid H2X are represented by the
constant of ammonia can be taken from
equations:
Table 6.7. Also, calculate the ionization
H2X(aq) H+(aq) + HX–(aq)
constant of the conjugate acid of ammonia.
HX–(aq) H+(aq) + X2–(aq)
Solution
And the corresponding equilibrium
The ionization of NH3 in water is represented constants are given below:
by equation:
Ka1= {[H+][HX–]} / [H2X] and

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 200 chemistry

Ka2 = {[H+][X2-]} / [HX-] In general, when strength of H-A bond

decreases, that is, the energy required to break
Here, Ka1and Ka2are called the first and second the bond decreases, HA becomes a stronger
ionization constants respectively of the acid H2 acid. Also, when the H-A bond becomes more
X. Similarly, for tribasic acids like H3PO4 we polar i.e., the electronegativity difference
have three ionization constants. The values between the atoms H and A increases and
of the ionization constants for some common there is marked charge separation, cleavage
polyprotic acids are given in Table 6.8. of the bond becomes easier thereby increasing
Table 6.8 The Ionization Constants of Some the acidity.
Common Polyprotic Acids (298K)
But it should be noted that while comparing
elements in the same group of the periodic
table, H-A bond strength is a more important
factor in determining acidity than its polar
nature. As the size of A increases down the
group, H-A bond strength decreases and so
the acid strength increases. For example,
Size increases
HF << HCl << HBr << HI
It can be seen that higher order ionization
constants (K a2, K a3) are smaller than the Acid strength increases
Similarly, H2S is stronger acid than H2O.
lower order ionization constant (K a1) of a
polyprotic acid. The reason for this is that But, when we discuss elements in the same
it is more difficult to remove a positively row of the periodic table, H-A bond polarity
charged proton from a negative ion due to becomes the deciding factor for determining
electrostatic forces. This can be seen in the the acid strength. As the electronegativity
case of removing a proton from the uncharged of A increases, the strength of the acid also
H2CO3 as compared from a negatively charged increases. For example,
HCO3–. Similarly, it is more difficult to remove
Electronegativity of A increases
a proton from a doubly charged HPO42– anion
as compared to H2PO4–. CH4 < NH3 < H2O < HF
Polyprotic acid solutions contain a Acid strength increases
mixture of acids like H2A, HA– and A2– in case
of a diprotic acid. H2A being a strong acid, the 6.11.8 Common Ion Effect in the
primary reaction involves the dissociation of Ionization of Acids and Bases
H2 A, and H3O+ in the solution comes mainly Consider an example of acetic acid dissociation
from the first dissociation step. equilibrium represented as:
CH3COOH(aq) H+(aq) + CH3COO– (aq)
6.11.7 Factors Affecting Acid Strength
Having discussed quantitatively the strengths or HAc(aq) H+ (aq) + Ac– (aq)
of acids and bases, we come to a stage where Ka = [H+][Ac– ] / [HAc]
we can calculate the pH of a given acid
Addition of acetate ions to an acetic
solution. But, the curiosity rises about why
acid solution results in decreasing the
should some acids be stronger than others?
concentration of hydrogen ions, [H+]. Also,
What factors are responsible for making
them stronger? The answer lies in its being a if H+ ions are added from an external source
complex phenomenon. But, broadly speaking then the equilibrium moves in the direction
we can say that the extent of dissociation of of undissociated acetic acid i.e., in a direction
an acid depends on the strength and polarity of reducing the concentration of hydrogen
of the H-A bond. ions, [H+]. This phenomenon is an example

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 EQUILIBRIUM 201

of common ion effect. It can be defined as

Thus, x = 1.33 × 10–3 = [OH–]
a shift in equilibrium on adding a substance
that provides more of an ionic species already Therefore, [H+] = Kw / [OH–] = 10–14 /
present in the dissociation equilibrium. (1.33 × 10–3) = 7.51 × 10–12
Thus, we can say that common ion effect is
a phenomenon based on the Le Chatelier’s pH = –log (7.5 × 10–12) = 11.12
principle discussed in section 6.8. On addition of 25 mL of 0.1M HCl
In order to evaluate the pH of the solution solution (i.e., 2.5 mmol of HCl) to 50
resulting on addition of 0.05M acetate ion to mL of 0.1M ammonia solution (i.e., 5
mmol of NH3), 2.5 mmol of ammonia
0.05M acetic acid solution, we shall consider
molecules are neutralized. The resulting
the acetic acid dissociation equilibrium once
75 mL solution contains the remaining
again, unneutralized 2.5 mmol of NH3 molecules
HAc(aq) H+(aq) + Ac–(aq) and 2.5 mmol of NH4+.
Initial concentration (M) NH3 + HCl → NH4+ + Cl–
0.05 0 0.05 2.5 2.5 0 0
Let x be the extent of ionization of acetic At equilibrium
acid. 0 0 2.5 2.5
Change in concentration (M) The resulting 75 mL of solution contains
2.5 mmol of NH4+ ions (i.e., 0.033 M) and
–x +x +x
2.5 mmol (i.e., 0.033 M ) of uneutralised
Equilibrium concentration (M) NH3 molecules. This NH3 exists in the
0.05-x x 0.05+x following equilibrium:
Therefore, NH4OH   NH4+ + OH–
Ka= [H+][Ac– ]/[H Ac] = {(0.05+x)(x)}/(0.05-x) 0.033M – y y y
where, y = [OH ] = [NH4 ]
– +
As Ka is small for a very weak acid, x<<0.05.
Hence, (0.05 + x) ≈ (0.05 – x) ≈ 0.05 The final 75 mL solution after
neutralisation already contains
Thus, 2.5 m mol NH4+ ions (i.e. 0.033M), thus
1.8 × 10–5 = (x) (0.05 + x) / (0.05 – x) total concentration of NH4+ ions is given
= x(0.05) / (0.05) = x = [H+] = 1.8 × 10–5M as:
[NH4+] = 0.033 + y
pH = – log(1.8 × 10–5) = 4.74
As y is small, [NH4OH]  0.033 M and
Problem 6.24 [NH4+]  0.033M.
We know,
Calculate the pH of a 0.10M ammonia
solution. Calculate the pH after 50.0 mL Kb = [NH4+][OH–] / [NH4OH]
of this solution is treated with 25.0 mL of = y (0.033)/(0.033) = 1.77 × 10–5 M
0.10M HCl. The dissociation constant of
ammonia, Kb = 1.77 × 10–5 Thus, y = 1.77 × 10–5 = [OH–]

Solution [H+] = 10–14 / 1.77 × 10–5 = 0.56 × 10–9

Hence, pH = 9.24
NH3 + H2O → NH4+ + OH–
Kb = [NH4+][OH–] / [NH3] = 1.77 × 10–5
Before neutralization, 6.11.9 Hydrolysis of Salts and the pH of
their Solutions
[NH4+] = [OH–] = x
[NH3] = 0.10 – x  0.10 Salts formed by the reactions between acids
and bases in definite proportions, undergo
x2 / 0.10 = 1.77 × 10–5
ionization in water. The cations/anions

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 202 chemistry

formed on ionization of salts either exist as increased of H+ ion concentration in solution

hydrated ions in aqueous solutions or interact making the solution acidic. Thus, the pH of
with water to reform corresponding acids/ NH4Cl solution in water is less than 7.
bases depending upon the nature of salts. Consider the hydrolysis of CH3COONH4
The later process of interaction between salt formed from weak acid and weak base.
water and cations/anions or both of salts The ions formed undergo hydrolysis as follow:
is called hydrolysis. The pH of the solution
gets affected by this interaction. The cations CH3COO– + NH4+ + H2O CH3COOH +
(e.g., Na+, K+, Ca2+, Ba2+, etc.) of strong bases NH4OH
and anions (e.g., Cl–, Br–, NO3–, ClO4– etc.) of CH3COOH and NH4OH, also remain into
strong acids simply get hydrated but do not partially dissociated form:
hydrolyse, and therefore the solutions of CH3COOH CH3COO– + H+
salts formed from strong acids and bases are
NH4OH NH4+ + OH–
neutral i.e., their pH is 7. However, the other
category of salts do undergo hydrolysis. H2O H+ + OH–
We now consider the hydrolysis of the Without going into detailed calculation,
salts of the following types : it can be said that degree of hydrolysis is
(i) salts of weak acid and strong base e.g., independent of concentration of solution, and
CH3COONa. pH of such solutions is determined by their
(ii) salts of strong acid and weak base e.g., pK values:
NH4Cl, and pH = 7 + ½ (pKa – pKb) (6.38)
(iii) salts of weak acid and weak base, e.g., The pH of solution can be greater than 7,
CH3COONH4. if the difference is positive and it will be less
In the first case, CH3COONa being a salt of than 7, if the difference is negative.
weak acid, CH3COOH and strong base, NaOH
Problem 6.25
gets completely ionised in aqueous solution.
The pKa of acetic acid and pKb of ammonium
CH3COONa(aq) → CH3COO– (aq)+ Na+(aq)
hydroxide are 4.76 and 4.75 respectively.
Acetate ion thus formed undergoes Calculate the pH of ammonium acetate
hydrolysis in water to give acetic acid and solution.
OH– ions
Solution
CH3COO–(aq)+H2O(l) CH3COOH(aq)+OH–(aq)
pH = 7 + ½ [pKa – pKb]
Acetic acid being a weak acid
= 7 + ½ [4.76 – 4.75]
(Ka = 1.8 × 10–5) remains mainly unionised in
solution. This results in increase of OH– ion = 7 + ½ [0.01] = 7 + 0.005 = 7.005
concentration in solution making it alkaline.
The pH of such a solution is more than 7. 6.12 BUFFER SOLUTIONS
Similarly, NH 4 Cl formed from weak Many body fluids e.g., blood or urine have
base, NH4OH and strong acid, HCl, in water definite pH and any deviation in their pH
dissociates completely. indicates malfunctioning of the body. The
+ control of pH is also very important in
NH4Cl(aq) → NH 4(aq) +Cl– (aq) many chemical and biochemical processes.
Ammonium ions undergo hydrolysis with Many medical and cosmetic formulations
water to form NH4OH and H+ ions require that these be kept and administered
+
NH 4 (aq) + H2O (1) NH4OH(aq) + H+(aq) at a particular pH. The solutions which
Ammonium hydroxide is a weak base resist change in pH on dilution or with
(K b = 1.77 × 10 –5) and therefore remains the addition of small amounts of acid or
almost unionised in solution. This results in alkali are called Buffer Solutions. Buffer

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 EQUILIBRIUM 203

solutions of known pH can be prepared from acid present in the mixture. Since acid is a
the knowledge of pKa of the acid or pKb of base weak acid, it ionises to a very little extent and
and by controlling the ratio of the salt and acid concentration of [HA] is negligibly different
or salt and base. A mixture of acetic acid and from concentration of acid taken to form
sodium acetate acts as buffer solution around buffer. Also, most of the conjugate base, [A—],
pH 4.75 and a mixture of ammonium chloride comes from the ionisation of salt of the acid.
and ammonium hydroxide acts as a buffer Therefore, the concentration of conjugate
around pH 9.25. You will learn more about base will be negligibly different from the
buffer solutions in higher classes. concentration of salt. Thus, equation (6.40)
takes the form:
6.12.1 Designing Buffer Solution
Knowledge of pK a , pK b and equilibrium [Salt]
pH=pK a + log
constant help us to prepare the buffer solution [Acid]
of known pH. Let us see how we can do this. In the equation (6.39), if the concentration
Preparation of Acidic Buffer of [A—] is equal to the concentration of [HA],
To prepare a buffer of acidic pH we use weak then pH = pKa because value of log 1 is zero.
acid and its salt formed with strong base. Thus if we take molar concentration of acid
and salt (conjugate base) same, the pH of the
We develop the equation relating the pH, the
buffer solution will be equal to the pKa of the
equilibrium constant, Ka of weak acid and
acid. So for preparing the buffer solution of
ratio of concentration of weak acid and its
the required pH we select that acid whose pKa
conjugate base. For the general case where
is close to the required pH. For acetic acid
the weak acid HA ionises in water,
pKa value is 4.76, therefore pH of the buffer
HA + H2O  H3O+ + A– solution formed by acetic acid and sodium
For which we can write the expression acetate taken in equal molar concentration
will be around 4.76.
A similar analysis of a buffer made with
a weak base and its conjugate acid leads to
Rearranging the expression we have,
the result,
[Conjugate acid,BH+ ]
pOH= pK b +log
[Base,B]
Taking logarithm on both the sides and (6.41)
rearranging the terms we get — pH of the buffer solution can be calculated
by using the equation pH + pOH =14.
We know that pH + pOH = pK w and
Or pKa + pKb = pKw. On putting these values in
equation (6.41) it takes the form as follows:
(6.39) [Conjugate acid,BH ]
pK w - pH = pK w  pK a  log
[Base,B]
or
[Conjugate acid,BH+ ]
pH = pK a + log
(6.40) [Base,B]
(6.42)
The expression (6.40) is known as If molar concentration of base and its
Henderson–Hasselbalch equation. The conjugate acid (cation) is same then pH of
the buffer solution will be same as pKa for the
quantity is the ratio of concentration base. pKa value for ammonia is s9.25; therefore
a buffer of pH close to 9.25 can be obtained
of conjugate base (anion) of the acid and the by taking ammonia solution and ammonium

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 204 chemistry

chloride solution of same molar concentration. We shall now consider the equilibrium
For a buffer solution formed by ammonium between the sparingly soluble ionic salt and
chloride and ammonium hydroxide, equation its saturated aqueous solution.
(6.42) becomes:
6.13.1 Solubility Product Constant
[Conjugate acid,BH+ ]
pH = 9.25 + log Let us now have a solid like barium sulphate
[Base,B] in contact with its saturated aqueous solution.
pH of the buffer solution is not affected by The equilibrium between the undisolved solid
dilution because ratio under the logarithmic and the ions in a saturated solution can be
term remains unchanged. represented by the equation:

6.13 SOLUBILITY EQUILIBRIA OF BaSO4(s)  Ba2+(aq) + SO42–(aq),

SPARINGLY SOLUBLE SALTS
We have already known that the solubility of The equilibrium constant is given by the
ionic solids in water varies a great deal. Some of equation:
these (like calcium chloride) are so soluble that K = {[Ba2+][SO42–]} / [BaSO4]
they are hygroscopic in nature and even absorb
For a pure solid substance the
water vapour from atmosphere. Others (such
concentration remains constant and we can
as lithium fluoride) have so little solubility
write
that they are commonly termed as insoluble.
The solubility depends on a number of factors Ksp = K[BaSO4] = [Ba2+][SO42–] (6.43)
important amongst which are the lattice We call Ksp the solubility product constant
enthalpy of the salt and the solvation enthalpy or simply solubility product. The experimental
of the ions in a solution. For a salt to dissolve value of Ksp in above equation at 298K is
in a solvent the strong forces of attraction 1.1 × 10–10. This means that for solid barium
between its ions (lattice enthalpy) must be sulphate in equilibrium with its saturated
overcome by the ion-solvent interactions. The solution, the product of the concentrations
solvation enthalpy of ions is referred to in of barium and sulphate ions is equal
terms of solvation which is always negative i.e. to its solubility product constant. The
energy is released in the process of solvation. concentrations of the two ions will be equal to
The amount of solvation enthalpy depends on the molar solubility of the barium sulphate.
the nature of the solvent. In case of a non- If molar solubility is S, then
polar (covalent) solvent, solvation enthalpy is
1.1 × 10–10 = (S)(S) = S2
small and hence, not sufficient to overcome
lattice enthalpy of the salt. Consequently, the or S = 1.05 × 10–5.
salt does not dissolve in non-polar solvent. As Thus, molar solubility of barium sulphate
a general rule, for a salt to be able to dissolve will be equal to 1.05 × 10–5 mol L–1.
in a particular solvent its solvation enthalpy A salt may give on dissociation two or
must be greater than its lattice enthalpy so more than two anions and cations carrying
that the latter may be overcome by former. different charges. For example, consider a salt
Each salt has its characteristic solubility which like zirconium phosphate of molecular formula
depends on temperature. We classify salts on (Zr4+)3(PO43–)4. It dissociates into 3 zirconium
the basis of their solubility in the following cations of charge +4 and 4 phosphate
three categories. anions of charge –3. If the molar solubility of
zirconium phosphate is S, then it can be seen
Category I Soluble Solubility > 0.1M from the stoichiometry of the compound that
Category II Slightly 0.01M<Solubility< 0.1M
[Zr4+] = 3S and [PO43–] = 4S
Soluble
Category III Sparingly Solubility < 0.01M and Ksp = (3S)3 (4S)4 = 6912 (S)7
Soluble or S = {Ksp / (33 × 44)}1/7 = (Ksp / 6912)1/7

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 EQUILIBRIUM 205

p q
A solid salt of the general formula M x X y Table 6.9 The Solubility Product Constants,
with molar solubility S in equilibrium with Ksp of Some Common Ionic Salts at
its saturated solution may be represented by 298K.
the equation:
MxXy(s) xMp+(aq) + yXq– (aq)
(where x × p = y × q–)
+

And its solubility product constant is

given by:
Ksp = [Mp+]x[Xq– ]y = (xS)x(yS)y (6.44)
= xx . yy . S(x + y)
S(x + y) = Ksp / xx . yy
S = (Ksp / xx . yy)1 / x + y (6.45)
The term Ksp in equation is given by Qsp
(section 6.6.2) when the concentration of one
or more species is not the concentration under
equilibrium. Obviously under equilibrium
conditions Ksp = Qsp but otherwise it gives the
direction of the processes of precipitation or
dissolution. The solubility product constants
of a number of common salts at 298K are
given in Table 6.9.

Problem 6.26
Calculate the solubility of A2 X3 in pure
water, assuming that neither kind of ion
reacts with water. The solubility product of
A2X3, Ksp = 1.1 × 10–23.
Solution
A2X3 → 2A3+ + 3X2–
Ksp = [A3+]2 [X2–]3 = 1.1 × 10–23
If S = solubility of A2X3, then
[A3+] = 2S; [X2–] = 3S
therefore, Ksp = (2S)2(3S)3 = 108S5
  = 1.1 × 10–23
thus, S5 = 1 × 10–25
S = 1.0 × 10–5 mol/L.
Problem 6.27
The values of Ksp of two sparingly soluble
salts Ni(OH)2 and AgCN are 2.0 × 10–15 and
6 × 0–17 respectively. Which salt is more
soluble? Explain.
Solution
AgCN Ag+ + CN–

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Unit [Link] 205 9/12/2022 [Link] AM

 206 chemistry

Ksp = [Ag+][CN–] = 6 × 10–17 Dissolution of S mol/L of Ni(OH)2 provides

Ni(OH)2 Ni2+ + 2OH– S mol/L of Ni2+ and 2S mol/L of OH–, but
the total concentration of OH– = (0.10 + 2S)
Ksp = [Ni ][OH–]2 = 2 × 10–15
2+
mol/L because the solution already contains
Let [Ag+] = S1, then [CN-] = S1 0.10 mol/L of OH– from NaOH.
Let [Ni2+] = S2, then [OH–] = 2S2
Ksp = 2.0 × 10–15 = [Ni2+] [OH–]2
S12 = 6 × 10–17 , S1 = 7.8 × 10–9
= (S) (0.10 + 2S)2
(S2)(2S2)2 = 2 × 10–15, S2 = 0.58 × 10–4
As Ksp is small, 2S << 0.10,
Ni(OH)2 is more soluble than AgCN.
thus, (0.10 + 2S) ≈ 0.10
6.13.2 Common Ion Effect on Solubility Hence,
of Ionic Salts 2.0 × 10–15 = S (0.10)2
It is expected from Le Chatelier’s principle S = 2.0 × 10–13 M = [Ni2+]
that if we increase the concentration of any
one of the ions, it should combine with the
ion of its opposite charge and some of the The solubility of salts of weak acids like
salt will be precipitated till once again Ksp = phosphates increases at lower pH. This is
Qsp. Similarly, if the concentration of one of because at lower pH the concentration of the
the ions is decreased, more salt will dissolve anion decreases due to its protonation. This
to increase the concentration of both the ions in turn increase the solubility of the salt so
till once again Ksp = Qsp. This is applicable that Ksp = Qsp. We have to satisfy two equilibria
even to soluble salts like sodium chloride simultaneously i.e.,
except that due to higher concentrations
of the ions, we use their activities instead Ksp = [M+] [X–],
of their molarities in the expression for
Qsp. Thus if we take a saturated solution of
sodium chloride and pass HCl gas through it,
then sodium chloride is precipitated due to
increased concentration (activity) of chloride
ion available from the dissociation of HCl. [X –] / [HX] = Ka/[H+]
Sodium chloride thus obtained is of very Taking inverse of both side and adding 1
high purity and we can get rid of impurities we get
like sodium and magnesium sulphates. The
common ion effect is also used for almost HX   1  H  
1
complete precipitation of a particular ion  X   Ka
as its sparingly soluble salt, with very low
HX   H   H   K a
value of solubility product for gravimetric   
estimation. Thus we can precipitate silver ion  X   Ka
as silver chloride, ferric ion as its hydroxide
(or hydrated ferric oxide) and barium ion as Now, again taking inverse, we get
its sulphate for quantitative estimations. [X–] / {[X–] + [HX]} = f = Ka/(Ka + [H+]) and it
can be seen that ‘f’ decreases as pH decreases.
Problem 6.28 If S is the solubility of the salt at a given
Calculate the molar solubility of Ni(OH)2 in pH then
0.10 M NaOH. The ionic product of Ni(OH)2
is 2.0 × 10–15. Ksp = [S] [f S] = S2 {Ka/(Ka + [H+])} and
S = {Ksp ([H+] + Ka)/Ka}1/2  (6.46)
Solution
Thus solubility S increases with increase
Let the solubility of Ni(OH)2 be equal to S. in [H+] or decrease in pH.

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Unit [Link] 206 9/12/2022 [Link] AM

 EQUILIBRIUM 207

SUMMARY

When the number of molecules leaving the liquid to vapour equals the number of molecules
returning to the liquid from vapour, equilibrium is said to be attained and is dynamic in
nature. Equilibrium can be established for both physical and chemical processes and at
this stage rate of forward and reverse reactions are equal. Equilibrium constant, Kc is
expressed as the concentration of products divided by reactants, each term raised to the
stoichiometric coefficient.

For reaction, a A + b B c C +d D
Kc = [C]c[D]d/[A]a[B]b
Equilibrium constant has constant value at a fixed temperature and at this stage all the
macroscopic properties such as concentration, pressure, etc. become constant. For a gaseous
reaction equilibrium constant is expressed as Kp and is written by replacing concentration
terms by partial pressures in Kc expression. The direction of reaction can be predicted by
reaction quotient Qc which is equal to Kc at equilibrium. Le Chatelier’s principle states that
the change in any factor such as temperature, pressure, concentration, etc. will cause the
equilibrium to shift in such a direction so as to reduce or counteract the effect of the change.
It can be used to study the effect of various factors such as temperature, concentration,
pressure, catalyst and inert gases on the direction of equilibrium and to control the yield of
products by controlling these factors. Catalyst does not effect the equilibrium composition
of a reaction mixture but increases the rate of chemical reaction by making available a new
lower energy pathway for conversion of reactants to products and vice-versa.

All substances that conduct electricity in aqueous solutions are called electrolytes. Acids,
bases and salts are electrolytes and the conduction of electricity by their aqueous solutions
is due to anions and cations produced by the dissociation or ionization of electrolytes
in aqueous solution. The strong electrolytes are completely dissociated. In weak electrolytes
there is equilibrium between the ions and the unionized electrolyte molecules. According to
Arrhenius, acids give hydrogen ions while bases produce hydroxyl ions in their aqueous
solutions. Brönsted-Lowry on the other hand, defined an acid as a proton donor and a base as
a proton acceptor. When a Brönsted-Lowry acid reacts with a base, it produces its conjugate
base and a conjugate acid corresponding to the base with which it reacts. Thus a conjugate
pair of acid-base differs only by one proton. Lewis further generalised the definition of an
acid as an electron pair acceptor and a base as an electron pair donor. The expressions
for ionization (equilibrium) constants of weak acids (Ka) and weak bases (Kb) are developed
using Arrhenius definition. The degree of ionization and its dependence on concentration and
common ion are discussed. The pH scale (pH = –log[H+]) for the hydrogen ion concentration
(activity) has been introduced and extended to other quantities (pOH = – log[OH–]); pKa = –log[Ka];
pKb = –log[Kb]; and pKw = –log[Kw] etc.). The ionization of water has been considered and we
note that the equation: pH + pOH = pKw is always satisfied. The salts of strong acid and
weak base, weak acid and strong base, and weak acid and weak base undergo hydrolysis in
aqueous solution. The definition of buffer solutions, and their importance are discussed
briefly. The solubility equilibrium of sparingly soluble salts is discussed and the equilibrium
constant is introduced as solubility product constant (Ksp). Its relationship with solubility
of the salt is established. The conditions of precipitation of the salt from their solutions
or their dissolution in water are worked out. The role of common ion and the solubility of
sparingly soluble salts is also discussed.

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Unit [Link] 207 9/12/2022 [Link] AM

 208 chemistry

SUGGESTED ACTIVITIES FOR STUDENTS REGARDING THIS UNIT

(a) The student may use pH paper in determining the pH of fresh juices of various vegetables
and fruits, soft drinks, body fluids and also that of water samples available.
(b) The pH paper may also be used to determine the pH of different salt solutions and from
that he/she may determine if these are formed from strong/weak acids and bases.
(c) They may prepare some buffer solutions by mixing the solutions of sodium acetate and
acetic acid and determine their pH using pH paper.
(d) They may be provided with different indicators to observe their colours in solutions of
varying pH.
(e) They may perform some acid-base titrations using indicators.
(f) They may observe common ion effect on the solubility of sparingly soluble salts.
(g) If pH meter is available in their school, they may measure the pH with it and compare
the results obtained with that of the pH paper.

EXERCISES

6.1 A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature.
The volume of the container is suddenly increased.

a) What is the initial effect of the change on vapour pressure?

b) How do rates of evaporation and condensation change initially?

c) What happens when equilibrium is restored finally and what will be the final vapour
pressure?

6.2 What is Kc for the following equilibrium when the equilibrium concentration of each
substance is: [SO2]= 0.60M, [O2] = 0.82M and [SO3] = 1.90M ?

2SO2(g) + O2(g) 2SO3(g)

6.3 At a certain temperature and total pressure of 105Pa, iodine vapour contains 40% by
volume of I atoms

I2 (g) 2I (g)
Calculate Kp for the equilibrium.

6.4 Write the expression for the equilibrium constant, Kc for each of the following reactions:

(i) 2NOCl (g) 2NO (g) + Cl2 (g)

(ii) 2Cu(NO3)2 (s) 2CuO (s) + 4NO2 (g) + O2 (g)
(iii) CH3COOC2H5(aq) + H2O(l) CH3COOH (aq) + C2H5OH (aq)
(iv) Fe 3+
(aq) + 3OH (aq)
–
Fe(OH)3 (s)
(v) I2 (s) + 5F2 2IF5
6.5 Find out the value of Kc for each of the following equilibria from the value of Kp:

(i) 2NOCl (g) 2NO (g) + Cl2 (g); Kp= 1.8 × 10–2 at 500 K
(ii) CaCO3 (s) CaO(s) + CO2(g); Kp= 167 at 1073 K

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Unit [Link] 208 9/12/2022 [Link] AM

 EQUILIBRIUM 209

6.6 For the following equilibrium, Kc= 6.3 × 1014 at 1000 K

NO (g) + O3 (g) NO2 (g) + O2 (g)
Both the forward and reverse reactions in the equilibrium are elementary bimolecular
reactions. What is Kc, for the reverse reaction?
6.7 Explain why pure liquids and solids can be ignored while writing the equilibrium
constant expression?

6.8 Reaction between N2 and O2– takes place as follows:

2N2 (g) + O2 (g) 2N2O (g)
If a mixture of 0.482 mol N2 and 0.933 mol of O2 is placed in a 10 L reaction vessel
and allowed to form N2O at a temperature for which Kc= 2.0 × 10–37, determine the
composition of equilibrium mixture.

6.9 Nitric oxide reacts with Br2 and gives nitrosyl bromide as per reaction given below:
2NO (g) + Br2 (g) 2NOBr (g)
When 0.087 mol of NO and 0.0437 mol of Br2 are mixed in a closed container at
constant temperature, 0.0518 mol of NOBr is obtained at equilibrium. Calculate
equilibrium amount of NO and Br2 .

6.10 At 450K, Kp= 2.0 × 1010/bar for the given reaction at equilibrium.
2SO2(g) + O2(g) 2SO3 (g)
What is Kc at this temperature ?

6.11 A sample of HI(g) is placed in flask at a pressure of 0.2 atm. At equilibrium the partial
pressure of HI(g) is 0.04 atm. What is Kp for the given equilibrium ?
2HI (g) H2 (g) + I2 (g)
6.12 A mixture of 1.57 mol of N2, 1.92 mol of H2 and 8.13 mol of NH3 is introduced into
a 20 L reaction vessel at 500 K. At this temperature, the equilibrium constant, Kc
for the reaction N2 (g) + 3H2 (g) 2NH3 (g) is 1.7 × 102. Is the reaction mixture at
equilibrium? If not, what is the direction of the net reaction?

6.13 The equilibrium constant expression for a gas reaction is,

NH3  O2 5
4

Kc 
NO4 H2O
6

Write the balanced chemical equation corresponding to this expression.

6.14 One mole of H2O and one mole of CO are taken in 10 L vessel and heated to
725 K. At equilibrium 40% of water (by mass) reacts with CO according to the equation,
H2O (g) + CO (g) H2 (g) + CO2 (g)
Calculate the equilibrium constant for the reaction.

6.15 At 700 K, equilibrium constant for the reaction:

H2 (g) + I2 (g) 2HI (g)
is 54.8. If 0.5 mol L of HI(g) is present at equilibrium at 700 K, what are the
–1

concentration of H2(g) and I2(g) assuming that we initially started with HI(g) and
allowed it to reach equilibrium at 700K?

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Unit [Link] 209 9/12/2022 [Link] AM

 210 chemistry

6.16 What is the equilibrium concentration of each of the substances in the equilibrium
when the initial concentration of ICl was 0.78 M ?
2ICl (g) I2 (g) + Cl2 (g); Kc = 0.14
6.17 Kp = 0.04 atm at 899 K for the equilibrium shown below. What is the equilibrium
concentration of C2H6 when it is placed in a flask at 4.0 atm pressure and allowed
to come to equilibrium?
C2H6 (g) C2H4 (g) + H2 (g)
6.18 Ethyl acetate is formed by the reaction between ethanol and acetic acid and the
equilibrium is represented as:
CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)
(i) Write the concentration ratio (reaction quotient), Qc, for this reaction (note: water
is not in excess and is not a solvent in this reaction)
(ii) At 293 K, if one starts with 1.00 mol of acetic acid and 0.18 mol of ethanol, there
is 0.171 mol of ethyl acetate in the final equilibrium mixture. Calculate the
equilibrium constant.
(iii) Starting with 0.5 mol of ethanol and 1.0 mol of acetic acid and maintaining it at
293 K, 0.214 mol of ethyl acetate is found after sometime. Has equilibrium been
reached?
6.19 A sample of pure PCl 5 was introduced into an evacuated vessel at 473
K. After equilibrium was attained, concentration of PCl 5 was found to be
0.5 × 10–1 mol L–1. If value of Kc is 8.3 × 10–3, what are the concentrations of PCl3 and
Cl2 at equilibrium?
PCl5 (g) PCl3 (g) + Cl2(g)
6.20 One of the reaction that takes place in producing steel from iron ore is the reduction
of iron(II) oxide by carbon monoxide to give iron metal and CO2.
FeO (s) + CO (g) Fe (s) + CO2 (g); Kp = 0.265 atm at 1050K

What are the equilibrium partial pressures of CO and CO2 at 1050 K if the initial
partial pressures are: pCO= 1.4 atm and = 0.80 atm?

6.21 Equilibrium constant, Kc for the reaction

N2 (g) + 3H2 (g) 2NH3 (g) at 500 K is 0.061

At a particular time, the analysis shows that composition of the reaction mixture is
3.0 mol L–1 N2, 2.0 mol L–1 H2 and 0.5 mol L–1 NH3. Is the reaction at equilibrium? If
not in which direction does the reaction tend to proceed to reach equilibrium?

6.22 Bromine monochloride, BrCl decomposes into bromine and chlorine and reaches the
equilibrium:
2BrCl (g) Br2 (g) + Cl2 (g)

for which Kc= 32 at 500 K. If initially pure BrCl is present at a concentration of

3.3 × 10–3 mol L–1, what is its molar concentration in the mixture at equilibrium?

6.23 At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in equilibrium with
soild carbon has 90.55% CO by mass
C (s) + CO2 (g) 2CO (g)

Calculate Kc for this reaction at the above temperature.

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Unit [Link] 210 9/12/2022 [Link] AM

 EQUILIBRIUM 211

6.24 Calculate a) ∆G and b) the equilibrium constant for the formation of NO2 from NO
and O2 at 298K
NO (g) + ½ O2 (g) NO2 (g)
where
∆fG (NO2) = 52.0 kJ/mol
∆fG (NO) = 87.0 kJ/mol
∆fG (O2) = 0 kJ/mol
6.25 Does the number of moles of reaction products increase, decrease or remain same
when each of the following equilibria is subjected to a decrease in pressure by
increasing the volume?
(a) PCl5 (g) PCl3 (g) + Cl2 (g)
(b) CaO (s) + CO2 (g) CaCO3 (s)
(c) 3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)
6.26 Which of the following reactions will get affected by increasing the pressure?
Also, mention whether change will cause the reaction to go into forward or
backward direction.
(i) COCl2 (g) CO (g) + Cl2 (g)
(ii) CH4 (g) + 2S2 (g) CS2 (g) + 2H2S (g)
(iii) CO2 (g) + C (s) 2CO (g)
(iv) 2H2 (g) + CO (g) CH3OH (g)
(v) CaCO3 (s) CaO (s) + CO2 (g)
(vi) 4 NH3 (g) + 5O2 (g) 4NO (g) + 6H2O(g)
6.27 The equilibrium constant for the following reaction is 1.6 ×105 at 1024K
H2(g) + Br2(g) 2HBr(g)
Find the equilibrium pressure of all gases if 10.0 bar of HBr is introduced into a
sealed container at 1024K.
6.28 Dihydrogen gas is obtained from natural gas by partial oxidation with steam as per
following endothermic reaction:
CH4 (g) + H2O (g) CO (g) + 3H2 (g)
(a) Write as expression for Kp for the above reaction.
(b) How will the values of Kp and composition of equilibrium mixture be
affected by
(i) increasing the pressure
(ii) increasing the temperature
(iii) using a catalyst?
6.29 Describe the effect of:
a) addition of H2
b) addition of CH3OH
c) removal of CO
d) removal of CH3OH
on the equilibrium of the reaction:
2H2(g) + CO (g) CH3OH (g)
6.30 At 473 K, equilibrium constant Kc for decomposition of phosphorus pentachloride,
PCl5 is 8.3 ×10-3. If decomposition is depicted as,

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Unit [Link] 211 9/12/2022 [Link] AM

 212 chemistry

PCl5 (g) PCl3 (g) + Cl2 (g) ∆rH  = 124.0 kJ mol–1

a) write an expression for Kc for the reaction.
b) what is the value of Kc for the reverse reaction at the same temperature?
c) what would be the effect on Kc if (i) more PCl5 is added (ii) pressure is increased
(iii) the temperature is increased ?
6.31 Dihydrogen gas used in Haber’s process is produced by reacting methane from
natural gas with high temperature steam. The first stage of two stage reaction
involves the formation of CO and H2. In second stage, CO formed in first stage is
reacted with more steam in water gas shift reaction,
CO (g) + H2O (g) CO2 (g) + H2 (g)
If a reaction vessel at 400 °C is charged with an equimolar mixture of CO and steam
such that pco = pH O = 4.0 bar, what will be the partial pressure of H2 at equilibrium?
2
Kp= 10.1 at 400°C
6.32 Predict which of the following reaction will have appreciable concentration of reactants
and products:
a) Cl2 (g) 2Cl (g) Kc = 5 ×10–39
b) Cl2 (g) + 2NO (g) 2NOCl (g) Kc = 3.7 × 108
c) Cl2 (g) + 2NO2 (g) 2NO2Cl (g) Kc = 1.8
6.33 The value of Kc for the reaction 3O2 (g) 2O3 (g) is 2.0 ×10–50 at 25°C. If the
equilibrium concentration of O2 in air at 25°C is 1.6 ×10–2, what is the concentration
of O3?
6.34 The reaction, CO(g) + 3H2(g) CH4(g) + H2O(g)
is at equilibrium at 1300 K in a 1L flask. It also contain 0.30 mol of CO, 0.10 mol of
H2 and 0.02 mol of H2O and an unknown amount of CH4 in the flask. Determine the
concentration of CH4 in the mixture. The equilibrium constant, Kc for the reaction
at the given temperature is 3.90.
6.35 What is meant by the conjugate acid-base pair? Find the conjugate acid/base for
the following species:
HNO2, CN–, HClO4, F –, OH–, CO , and S2–
6.36 Which of the followings are Lewis acids? H2O, BF3, H+, and NH4+
6.37 What will be the conjugate bases for the Brönsted acids: HF, H2SO4 and HCO–3?
6.38 Write the conjugate acids for the following Brönsted bases: NH2–, NH3 and HCOO–.
6.39 The species: H2O, HCO3–, HSO4– and NH3 can act both as Brönsted acids and bases.
For each case give the corresponding conjugate acid and base.
6.40 Classify the following species into Lewis acids and Lewis bases and show how these
act as Lewis acid/base: (a) OH – (b) F – (c) H+ (d) BCl3 .
6.41 The concentration of hydrogen ion in a sample of soft drink is 3.8 × 10–3 M. What is
its pH?
6.42 The pH of a sample of vinegar is 3.76. Calculate the concentration of hydrogen ion
in it.
6.43 The ionization constant of HF, HCOOH and HCN at 298K are 6.8 × 10 –4,
1.8 × 10–4 and 4.8 × 10–9 respectively. Calculate the ionization constants of the
corresponding conjugate base.

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Unit [Link] 212 11/30/2022 [Link]

 EQUILIBRIUM 213

6.44 The ionization constant of phenol is 1.0 × 10–10. What is the concentration of phenolate
ion in 0.05 M solution of phenol? What will be its degree of ionization if the solution
is also 0.01M in sodium phenolate?
6.45 The first ionization constant of H2S is 9.1 × 10–8. Calculate the concentration
of HS– ion in its 0.1M solution. How will this concentration be affected if the
solution is 0.1M in HCl also? If the second dissociation constant of H 2S is
1.2 × 10–13, calculate the concentration of S2– under both conditions.
6.46 The ionization constant of acetic acid is 1.74 × 10–5. Calculate the degree of
dissociation of acetic acid in its 0.05 M solution. Calculate the concentration of
acetate ion in the solution and its pH.
6.47 It has been found that the pH of a 0.01M solution of an organic acid is 4.15. Calculate
the concentration of the anion, the ionization constant of the acid and its pKa.
6.48 Assuming complete dissociation, calculate the pH of the following solutions:
(a) 0.003 M HCl (b) 0.005 M NaOH (c) 0.002 M HBr (d) 0.002 M KOH
6.49 Calculate the pH of the following solutions:
a) 2 g of TlOH dissolved in water to give 2 litre of solution.
b) 0.3 g of Ca(OH)2 dissolved in water to give 500 mL of solution.
c) 0.3 g of NaOH dissolved in water to give 200 mL of solution.
d) 1mL of 13.6 M HCl is diluted with water to give 1 litre of solution.
6.50 The degree of ionization of a 0.1M bromoacetic acid solution is 0.132. Calculate the
pH of the solution and the pKa of bromoacetic acid.
6.51 The pH of 0.005M codeine (C18H21NO3) solution is 9.95. Calculate its ionization
constant and pKb.
6.52 What is the pH of 0.001M aniline solution? The ionization constant of aniline
can be taken from Table 6.7. Calculate the degree of ionization of aniline in the
solution. Also calculate the ionization constant of the conjugate acid of aniline.
6.53 Calculate the degree of ionization of 0.05M acetic acid if its pKa value is 4.74.
How is the degree of dissociation affected when its solution also contains
(a) 0.01M (b) 0.1M in HCl ?
6.54 The ionization constant of dimethylamine is 5.4 × 10–4. Calculate its degree of
ionization in its 0.02M solution. What percentage of dimethylamine is ionized if the
solution is also 0.1M in NaOH?
6.55 Calculate the hydrogen ion concentration in the following biological fluids whose
pH are given below:
(a) Human muscle-fluid, 6.83 (b) Human stomach fluid, 1.2
(c) Human blood, 7.38 (d) Human saliva, 6.4.
6.56 The pH of milk, black coffee, tomato juice, lemon juice and egg white are 6.8, 5.0,
4.2, 2.2 and 7.8 respectively. Calculate corresponding hydrogen ion concentration
in each.
6.57 If 0.561 g of KOH is dissolved in water to give 200 mL of solution at 298 K. Calculate
the concentrations of potassium, hydrogen and hydroxyl ions. What is its pH?
6.58 The solubility of Sr(OH)2 at 298 K is 19.23 g/L of solution. Calculate the concentrations
of strontium and hydroxyl ions and the pH of the solution.

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Unit [Link] 213 11/30/2022 [Link]

 214 chemistry

6.59 The ionization constant of propanoic acid is 1.32 × 10–5. Calculate the degree of
ionization of the acid in its 0.05M solution and also its pH. What will be its degree
of ionization if the solution is 0.01M in HCl also?
6.60 The pH of 0.1M solution of cyanic acid (HCNO) is 2.34. Calculate the ionization
constant of the acid and its degree of ionization in the solution.
6.61 The ionization constant of nitrous acid is 4.5 × 10–4. Calculate the pH of 0.04 M
sodium nitrite solution and also its degree of hydrolysis.
6.62 A 0.02M solution of pyridinium hydrochloride has pH = 3.44. Calculate the ionization
constant of pyridine.
6.63 Predict if the solutions of the following salts are neutral, acidic or basic:
NaCl, KBr, NaCN, NH4NO3, NaNO2 and KF
6.64 The ionization constant of chloroacetic acid is 1.35 × 10–3. What will be the pH of
0.1M acid and its 0.1M sodium salt solution?
6.65 Ionic product of water at 310 K is 2.7 × 10–14. What is the pH of neutral water at
this temperature?
6.66 Calculate the pH of the resultant mixtures:
a) 10 mL of 0.2M Ca(OH)2 + 25 mL of 0.1M HCl
b) 10 mL of 0.01M H2SO4 + 10 mL of 0.01M Ca(OH)2
c) 10 mL of 0.1M H2SO4 + 10 mL of 0.1M KOH
6.67 Determine the solubilities of silver chromate, barium chromate, ferric hydroxide,
lead chloride and mercurous iodide at 298K from their solubility product constants
given in Table 6.9. Determine also the molarities of individual ions.
6.68 The solubility product constant of Ag 2CrO 4 and AgBr are 1.1 × 10 –12 and
5.0 × 10–13 respectively. Calculate the ratio of the molarities of their saturated
solutions.
6.69 Equal volumes of 0.002 M solutions of sodium iodate and cupric chlorate are
mixed together. Will it lead to precipitation of copper iodate? (For cupric iodate
Ksp = 7.4 × 10–8 ).
6.70 The ionization constant of benzoic acid is 6.46 × 10–5 and Ksp for silver benzoate is
2.5 × 10–13. How many times is silver benzoate more soluble in a buffer of pH 3.19
compared to its solubility in pure water?
6.71 What is the maximum concentration of equimolar solutions of ferrous sulphate and
sodium sulphide so that when mixed in equal volumes, there is no precipitation of
iron sulphide? (For iron sulphide, Ksp = 6.3 × 10–18).
6.72 What is the minimum volume of water required to dissolve 1g of calcium sulphate
at 298 K? (For calcium sulphate, Ksp is 9.1 × 10–6).
6.73 The concentration of sulphide ion in 0.1M HCl solution saturated with hydrogen
sulphide is 1.0 × 10–19 M. If 10 mL of this is added to 5 mL of 0.04 M solution of the
following: FeSO4, MnCl2, ZnCl2 and CdCl2. in which of these solutions precipitation
will take place?

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Unit [Link] 214 11/30/2022 [Link]

 redox reactions 235

Unit 7

redox reactions

Where there is oxidation, there is always reduction –

Chemistry is essentially a study of redox systems.

After studying this unit you will be

able to Chemistry deals with varieties of matter and change
of one kind of matter into the other. Transformation of
• identify redox reactions as a class
of reactions in which oxidation matter from one kind into another occurs through the
and reduction reactions occur various types of reactions. One important category of such
simultaneously; reactions is Redox Reactions. A number of phenomena,
• define the terms oxidation, both physical as well as biological, are concerned with
reduction, oxidant (oxidising redox reactions. These reactions find extensive use in
agent) and reductant (reducing pharmaceutical, biological, industrial, metallurgical and
agent); agricultural areas. The importance of these reactions is
• explain mechanism of redox apparent from the fact that burning of different types of
reactions by electron transfer fuels for obtaining energy for domestic, transport and
process;
other commercial purposes, electrochemical processes
• use the concept of oxidation for extraction of highly reactive metals and non-metals,
number to identify oxidant and manufacturing of chemical compounds like caustic
reductant in a reaction;
soda, operation of dry and wet batteries and corrosion of
• classify redox reaction into metals fall within the purview of redox processes. Of late,
combination (synthesis),
decomposition, displacement
environmental issues like Hydrogen Economy (use of
and disproportionation liquid hydrogen as fuel) and development of ‘Ozone Hole’
reactions; have started figuring under redox phenomenon.
• suggest a comparative order
7.1 CLASSICAL IDEA OF REDOX REACTIONS –
among various reductants and
oxidants; OXIDATION AND REDUCTION REACTIONS
• balance chemical equations Originally, the term oxidation was used to describe the
using (i) oxidation number addition of oxygen to an element or a compound. Because
(ii) half reaction method; of the presence of dioxygen in the atmosphere (~20%),
• lear n the concept of redox many elements combine with it and this is the principal
reactions in terms of electrode reason why they commonly occur on the earth in the
processes. form of their oxides. The following reactions represent
oxidation processes according to the limited definition of
oxidation:
2 Mg (s) + O2 (g) → 2 MgO (s) (7.1)
S (s) + O2 (g) → SO2 (g) (7.2)

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 236 chemistry

In reactions (7.1) and (7.2), the elements broadened these days to include removal
magnesium and sulphur are oxidised on of oxygen/electronegative element from
account of addition of oxygen to them. a substance or addition of hydrogen/
Similarly, methane is oxidised owing to the electropositive element to a substance.
addition of oxygen to it. According to the definition given above,
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) (7.3) the following are the examples of reduction
processes:
A careful examination of reaction (7.3) in
which hydrogen has been replaced by oxygen 2 HgO (s) 2 Hg (l) + O2 (g) (7.8)
prompted chemists to reinterpret oxidation (removal of oxygen from mercuric oxide )
in terms of removal of hydrogen from it and, 2 FeCl3 (aq) + H2 (g) →2 FeCl2 (aq) + 2 HCl(aq)
therefore, the scope of term oxidation was (7.9)
broadened to include the removal of hydrogen
from a substance. The following illustration is (removal of electronegative element, chlorine
another reaction where removal of hydrogen from ferric chloride)
can also be cited as an oxidation reaction. CH2 = CH2 (g) + H2 (g) → H3C – CH3 (g) (7.10)
(addition of hydrogen)
2 H2S(g) + O2 (g) → 2 S (s) + 2 H2O (l) (7.4)
2HgCl2 (aq) + SnCl2 (aq) → Hg2Cl2 (s)+SnCl4 (aq)
As knowledge of chemists grew, it was
natural to extend the term oxidation for (7.11)
reactions similar to (7.1 to 7.4), which do (addition of mercury to mercuric chloride)
not involve oxygen but other electronegative In reaction (7.11) simultaneous oxidation
elements. The oxidation of magnesium with of stannous chloride to stannic chloride is
fluorine, chlorine and sulphur etc. occurs also occurring because of the addition of
according to the following reactions : electronegative element chlorine to it. It was
soon realised that oxidation and reduction
Mg (s) + F2 (g) → MgF2 (s) (7.5)
always occur simultaneously (as will be
Mg (s) + Cl2 (g) → MgCl2 (s) (7.6) apparent by re-examining all the equations
given above), hence, the word “redox” was
Mg (s) + S (s) → MgS (s) (7.7) coined for this class of chemical reactions.
Incorporating the reactions (7.5 to Problem 7.1
7.7) within the fold of oxidation reactions
In the reactions given below, identify
encouraged chemists to consider not only
the species undergoing oxidation and
the removal of hydrogen as oxidation, but
reduction:
also the removal of electropositive elements
as oxidation. Thus the reaction : (i) H2S (g) + Cl2 (g) → 2 HCl (g) + S (s)

2K4 [Fe(CN)6](aq) + H2O2 (aq) →2K3[Fe(CN)6](aq) (ii) 3Fe3O4 (s) + 8 Al (s) → 9 Fe (s)
+ 2 KOH (aq) + 4Al2O3 (s)
is interpreted as oxidation due to the removal (iii) 2 Na (s) + H2 (g) → 2 NaH (s)
of electropositive element potassium from
Solution
potassium ferrocyanide before it changes to
potassium ferricyanide. To summarise, the (i) H 2 S is oxidised because a more
term “oxidation” is defined as the addition electronegative element, chlorine is added
of oxygen/electronegative element to to hydrogen (or a more electropositive
a substance or removal of hydrogen/ element, hydrogen has been removed
electropositive element from a substance. from S). Chlorine is reduced due to
addition of hydrogen to it.
In the beginning, reduction was considered
as removal of oxygen from a compound. (ii) Aluminium is oxidised because
However, the term reduction has been oxygen is added to it. Ferrous ferric oxide

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 redox reactions 237

For convenience, each of the above

(Fe3O4) is reduced because oxygen has
processes can be considered as two separate
been removed from it.
steps, one involving the loss of electrons
(iii) With the careful application of the and the other the gain of electrons. As an
concept of electronegativity only we illustration, we may further elaborate one of
may infer that sodium is oxidised and these, say, the formation of sodium chloride.
hydrogen is reduced.
2 Na(s) → 2 Na+(g) + 2e–
Reaction (iii) chosen here prompts us to
think in terms of another way to define Cl2(g) + 2e– → 2 Cl–(g)
redox reactions. Each of the above steps is called a half
reaction, which explicitly shows involvement
7.2 REDOX REACTIONS IN TERMS OF of electrons. Sum of the half reactions gives
ELECTRON TRANSFER REACTIONS the overall reaction :
We have already learnt that the reactions
2 Na(s) + Cl2 (g) → 2 Na+ Cl– (s) or 2 NaCl (s)
2Na(s) + Cl2(g) → 2NaCl (s) (7.12)
Reactions 7.12 to 7.14 suggest that half
4Na(s) + O2(g) → 2Na2O(s) (7.13) reactions that involve loss of electrons are
2Na(s) + S(s) → Na2S(s) (7.14) called oxidation reactions. Similarly, the
are redox reactions because in each of these half reactions that involve gain of electrons
reactions sodium is oxidised due to the addition are called reduction reactions. It may not
of either oxygen or more electronegative be out of context to mention here that the
element to sodium. Simultaneously, chlorine, new way of defining oxidation and reduction
oxygen and sulphur are reduced because to has been achieved only by establishing a
each of these, the electropositive element correlation between the behaviour of species
sodium has been added. From our knowledge as per the classical idea and their interplay
of chemical bonding we also know that sodium in electron-transfer change. In reactions (7.12
chloride, sodium oxide and sodium sulphide to 7.14) sodium, which is oxidised, acts as
are ionic compounds and perhaps better a reducing agent because it donates electron
written as Na+Cl– (s), (Na+)2O2–(s), and (Na+)2 to each of the elements interacting with it and
S2–(s). Development of charges on the species thus helps in reducing them. Chlorine, oxygen
produced suggests us to rewrite the reactions and sulphur are reduced and act as oxidising
(7.12 to 7.14) in the following manner : agents because these accept electrons from
sodium. To summarise, we may mention that
Oxidation : Loss of electron(s) by any species.
Reduction : Gain of electron(s) by any species.
Oxidising agent : Acceptor of electron(s).
Reducing agent : Donor of electron(s).

Problem 7.2 Justify that the reaction:

2 Na(s) + H2(g) → 2 NaH (s) is a redox
change.
Solution
Since in the above reaction the compound
formed is an ionic compound, which may
also be represented as Na+H– (s), this
suggests that one half reaction in this
process is :
2 Na (s) → 2 Na+(g) + 2e–

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 238 chemistry

and the other half reaction is: At this stage we may investigate the state
H2 (g) + 2e– → 2 H–(g) of equilibrium for the reaction represented by
equation (7.15). For this purpose, let us place
This splitting of the reaction under a strip of metallic copper in a zinc sulphate
examination into two half reactions solution. No visible reaction is noticed and
automatically reveals that here sodium attempt to detect the presence of Cu2+ ions
is oxidised and hydrogen is reduced, by passing H2S gas through the solution to
therefore, the complete reaction is a produce the black colour of cupric sulphide,
redox change. CuS, does not succeed. Cupric sulphide has
such a low solubility that this is an extremely
7.2.1 Competitive Electron Transfer
sensitive test; yet the amount of Cu2+ formed
Reactions
cannot be detected. We thus conclude that
Place a strip of metallic zinc in an aqueous
the state of equilibrium for the reaction (7.15)
solution of copper nitrate as shown in Fig.
greatly favours the products over the reactants.
7.1, for about one hour. You may notice
that the strip becomes coated with reddish Let us extend electron transfer reaction
metallic copper and the blue colour of the now to copper metal and silver nitrate solution
solution disappears. Formation of Zn2+ ions in water and arrange a set-up as shown in
among the products can easily be judged Fig. 7.2. The solution develops blue colour
when the blue colour of the solution due to due to the formation of Cu2+ ions on account
Cu2+ has disappeared. If hydrogen sulphide of the reaction:
gas is passed through the colourless solution
containing Zn2+ ions, appearance of white zinc
sulphide, ZnS can be seen on making the
solution alkaline with ammonia.
The reaction between metallic zinc and the (7.16)
aqueous solution of copper nitrate is :
Here, Cu(s) is oxidised to Cu 2+ (aq) and
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) (7.15)
Ag+(aq) is reduced to Ag(s). Equilibrium greatly
In reaction (7.15), zinc has lost electrons favours the products Cu2+ (aq) and Ag(s).
to form Zn2+ and, therefore, zinc is oxidised. By way of contrast, let us also compare
Evidently, now if zinc is oxidised, releasing the reaction of metallic cobalt placed in nickel
electrons, something must be reduced, sulphate solution. The reaction that occurs
accepting the electrons lost by zinc. Copper here is :
ion is reduced by gaining electrons from the zinc.
Reaction (7.15) may be rewritten as :

(7.17)

Fig. 7.1 Redox reaction between zinc and aqueous solution of copper nitrate occurring in a beaker.

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 redox reactions 239

Fig. 7.2 Redox reaction between copper and aqueous solution of silver nitrate occurring in a beaker.

At equilibrium, chemical tests reveal that both However, as we shall see later, the charge
Ni2+(aq) and Co2+(aq) are present at moderate transfer is only partial and is perhaps better
concentrations. In this case, neither the described as an electron shift rather than a
reactants [Co(s) and Ni2+(aq)] nor the products complete loss of electron by H and gain by
[Co2+(aq) and Ni (s)] are greatly favoured. O. What has been said here with respect
This competition for release of electrons to equation (7.18) may be true for a good
incidently reminds us of the competition for number of other reactions involving covalent
release of protons among acids. The similarity compounds. Two such examples of this class
suggests that we might develop a table in of the reactions are:
which metals and their ions are listed on the H2(s) + Cl2(g) → 2HCl(g) (7.19)
basis of their tendency to release electrons and,
just as we do in the case of acids to indicate
CH 4(g) + 4Cl2(g) → CCl4(l) + 4HCl(g) (7.20)
the strength of the acids. As a matter of fact
we have already made certain comparisons. In order to keep track of electron shifts
By comparison we have come to know that in chemical reactions involving formation
zinc releases electrons to copper and copper of covalent compounds, a more practical
releases electrons to silver and, therefore, method of using oxidation number has
the electron releasing tendency of the metals been developed. In this method, it is always
is in the order: Zn>Cu>Ag. We would love to assumed that there is a complete transfer
make our list more vast and design a metal of electron from a less electronegative atom
activity series or electrochemical series. to a more electonegative atom. For example,
The competition for electrons between various we rewrite equations (7.18 to 7.20) to show
metals helps us to design a class of cells, charge on each of the atoms forming part of
named as Galvanic cells in which the chemical the reaction :
reactions become the source of electrical 0 0 +1 –2

energy. We would study more about these 2H2(g) + O2(g) → 2H2O (l) (7.21)
cells in Class XII. 0 0 +1 –1
H2 (s) + Cl2(g) → 2HCl(g) (7.22)
7.3 OXIDATION NUMBER
–4+1 0 +4 –1 +1 –1
A less obvious example of electron transfer is
realised when hydrogen combines with oxygen CH4(g) + 4Cl2(g) → CCl4(l) +4HCl(g) (7.23)
to form water by the reaction: It may be emphasised that the assumption
2H2(g) + O2 (g) → 2H2O (l) (7.18) of electron transfer is made for book-keeping
Though not simple in its approach, yet purpose only and it will become obvious at
we can visualise the H atom as going from a a later stage in this unit that it leads to the
neutral (zero) state in H2 to a positive state in simple description of redox reactions.
H2O, the O atom goes from a zero state in O2 Oxidation number denotes the oxidation
to a dinegative state in H2O. It is assumed that state of an element in a compound
there is an electron transfer from H to O and ascertained according to a set of rules
consequently H2 is oxidised and O2 is reduced. formulated on the basis that electron pair

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 240 chemistry

in a covalent bond belongs entirely to more bonding state of oxygen but this number
electronegative element. would now be a positive figure only.
It is not always possible to remember or 4. The oxidation number of hydrogen is +1,
make out easily in a compound/ion, which except when it is bonded to metals in binary
element is more electronegative than the compounds (that is compounds containing
other. Therefore, a set of rules has been two elements). For example, in LiH, NaH,
formulated to determine the oxidation and CaH2, its oxidation number is –1.
number of an element in a compound/ion. 5. In all its compounds, fluorine has an
If two or more than two atoms of an element oxidation number of –1. Other halogens (Cl,
are present in the molecule/ion such as Br, and I) also have an oxidation number
Na2S2O3/Cr2O72–, the oxidation number of the of –1, when they occur as halide ions in
atom of that element will then be the average their compounds. Chlorine, bromine and
of the oxidation number of all the atoms of iodine when combined with oxygen, for
that element. We may at this stage, state the example in oxoacids and oxoanions, have
rules for the calculation of oxidation number. positive oxidation numbers.
These rules are: 6. The algebraic sum of the oxidation number
of all the atoms in a compound must be
1. In elements, in the free or the uncombined
zero. In polyatomic ion, the algebraic sum
state, each atom bears an oxidation
of all the oxidation numbers of atoms of
number of zero. Evidently each atom in
the ion must equal the charge on the ion.
H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has the
Thus, the sum of oxidation number of three
oxidation number zero. oxygen atoms and one carbon atom in the
2. For ions composed of only one atom, the carbonate ion, (CO3)2– must equal –2.
oxidation number is equal to the charge By the application of above rules, we can
on the ion. Thus Na+ ion has an oxidation find out the oxidation number of the desired
number of +1, Mg2+ ion, +2, Fe3+ ion, +3, element in a molecule or in an ion. It is clear
Cl– ion, –1, O2– ion, –2; and so on. In their that the metallic elements have positive
compounds all alkali metals have oxidation oxidation number and nonmetallic elements
number of +1, and all alkaline earth metals have positive or negative oxidation number.
have an oxidation number of +2. Aluminium The atoms of transition elements usually
is regarded to have an oxidation number of display several positive oxidation states. The
+3 in all its compounds. highest oxidation number of a representative
3. The oxidation number of oxygen in most element is the group number for the first
compounds is –2. However, we come two groups and the group number minus 10
across two kinds of exceptions here. (following the long form of periodic table) for
One arises in the case of peroxides and the other groups. Thus, it implies that the
superoxides, the compounds of oxygen in highest value of oxidation number exhibited
which oxygen atoms are directly linked to by an atom of an element generally increases
each other. While in peroxides (e.g., H2O2, across the period in the periodic table. In the
Na2O2), each oxygen atom is assigned an third period, the highest value of oxidation
oxidation number of –1, in superoxides number changes from 1 to 7 as indicated
(e.g., KO2, RbO2) each oxygen atom is below in the compounds of the elements.
assigned an oxidation number of –(½). A term that is often used interchangeably
The second exception appears rarely, i.e. with the oxidation number is the oxidation
when oxygen is bonded to fluorine. In state. Thus in CO2, the oxidation state of
such compounds e.g., oxygen difluoride carbon is +4, that is also its oxidation number
(OF2) and dioxygen difluoride (O2F2), the and similarly the oxidation state as well
oxygen is assigned an oxidation number as oxidation number of oxygen is – 2. This
of +2 and +1, respectively. The number implies that the oxidation number denotes the
assigned to oxygen will depend upon the oxidation state of an element in a compound.

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 redox reactions 241

Group 1 2 13 14 15 16 17
Element Na Mg Al Si P S Cl
Compound NaCl MgSO4 AlF3 SiCl4 P4O10 SF6 HClO
Highest oxidation +1 +2 +3 +4 +5 +6 +7
number state of
the group element

The oxidation number/state of a metal in a The idea of oxidation number has been
compound is sometimes presented according invariably applied to define oxidation,
to the notation given by German chemist, reduction, oxidising agent (oxidant), reducing
Alfred Stock. It is popularly known as Stock agent (reductant) and the redox reaction. To
notation. According to this, the oxidation summarise, we may say that:
number is expressed by putting a Roman Oxidation: An increase in the oxidation
numeral representing the oxidation number
number of the element in the given substance.
in parenthesis after the symbol of the metal in
the molecular formula. Thus aurous chloride Reduction : A decrease in the oxidation
and auric chloride are written as Au(I)Cl and number of the element in the given substance.
Au(III)Cl3. Similarly, stannous chloride and Oxidising agent: A reagent which can
stannic chloride are written as Sn(II)Cl2 and increase the oxidation number of an element
Sn(IV)Cl4. This change in oxidation number in a given substance. These reagents are
implies change in oxidation state, which in called as oxidants also.
turn helps to identify whether the species Reducing agent: A reagent which lowers the
is present in oxidised form or reduced form. oxidation number of an element in a given
Thus, Hg2(I)Cl2 is the reduced form of Hg(II) Cl2. substance. These reagents are also called as
Problem 7.3 reductants.
Using Stock notation, represent the Redox reactions: Reactions which involve
following compounds :HAuCl4, Tl2O, FeO, change in oxidation number of the interacting
Fe2O3, CuI, CuO, MnO and MnO2. species.
Solution Problem 7.4
By applying various rules of calculating Justify that the reaction:
the oxidation number of the desired
element in a compound, the oxidation 2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2(g)
number of each metallic element in its is a redox reaction. Identify the species
compound is as follows: oxidised/reduced, which acts as an
HAuCl4 → Au has 3 oxidant and which acts as a reductant.
Tl2O → Tl has 1 Solution
FeO → Fe has 2 Let us assign oxidation number to each
Fe2O3 → Fe has 3 of the species in the reaction under
CuI → Cu has 1 examination. This results into:
CuO → Cu has 2 +1 –2 +1 –2 0 +4 –2
MnO → Mn has 2 2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2
MnO2 → Mn has 4
We therefore, conclude that in this
Therefore, these compounds may be reaction copper is reduced from +1 state
represented as: to zero oxidation state and sulphur is
HAu(III)Cl4, Tl2(I)O, Fe(II)O, Fe 2(III)O3, oxidised from –2 state to +4 state. The
Cu(I)I, Cu(II)O, Mn(II)O, Mn(IV)O2. above reaction is thus a redox reaction.

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 242 chemistry

here that all decomposition reactions are not

Further, Cu2O helps sulphur in Cu2S to
redox reactions. For example, decomposition
increase its oxidation number, therefore,
of calcium carbonate is not a redox reaction.
Cu(I) is an oxidant; and sulphur of Cu2S
+2 +4 –2 +2 –2 +4 –2
helps copper both in Cu2S itself and
Cu2O to decrease its oxidation number; CaCO3 (s) CaO(s) + CO2(g)
therefore, sulphur of Cu2S is reductant. 3. Displacement reactions
In a displacement reaction, an ion (or an
7.3.1 Types of Redox Reactions atom) in a compound is replaced by an ion
(or an atom) of another element. It may be
1. Combination reactions
denoted as:
A combination reaction may be denoted in
X + YZ → XZ + Y
the manner:
A+B → C Displacement reactions fit into two
Either A and B or both A and B must be in categories: metal displacement and non-metal
the elemental form for such a reaction to be displacement.
a redox reaction. All combustion reactions, (a) Metal displacement: A metal in a
which make use of elemental dioxygen, as well compound can be displaced by another metal
as other reactions involving elements other in the uncombined state. We have already
than dioxygen, are redox reactions. Some discussed about this class of the reactions
important examples of this category are: under section 7.2.1. Metal displacement
0 0 +4 –2 reactions find many applications in
C(s) + O2 (g) CO2(g) (7.24) metallurgical processes in which pure metals
are obtained from their compounds in ores. A
0 0 +2 –3
few such examples are:
3Mg(s) + N2(g) Mg3N2(s) (7.25)
+2 +6 –2 0 0 +2 +6 –2
–4+1 0 +4 –2 +1 –2
CuSO4(aq) + Zn (s) → Cu(s) + ZnSO4 (aq)
CH4(g) + 2O2(g) CO2(g) + 2H2O (l) (7.29)
2. Decomposition reactions +5 –2 0 0 +2 –2
V2O5 (s) + 5Ca (s) 2V (s) + 5CaO (s)
Decomposition reactions are the opposite
of combination reactions. Precisely, a (7.30)
decomposition reaction leads to the breakdown +4 –1 0 0 +2 –1
of a compound into two or more components TiCl4 (l) + 2Mg (s) Ti (s) + 2 MgCl2 (s)
at least one of which must be in the elemental
(7.31)
state. Examples of this class of reactions are:
+1 –2 0 0 +3 –2 0 +3 –2 0

2H2O (l) 2H2 (g) + O2(g) (7.26) Cr2O3 (s) + 2 Al (s) Al2O3 (s) + 2Cr(s)
(7.32)
+1 –1 0 0
In each case, the reducing metal is a
2NaH (s) 2Na (s) + H2(g) (7.27)
better reducing agent than the one that is
+1 +5 –2 +1 –1 0 being reduced which evidently shows more
2KClO3 (s) 2KCl (s) + 3O2(g) (7.28) capability to lose electrons as compared to
It may carefully be noted that there is no the one that is reduced.
change in the oxidation number of hydrogen (b) Non-metal displacement: The non-
in methane under combination reactions metal displacement redox reactions include
and that of potassium in potassium chlorate hydrogen displacement and a rarely occurring
in reaction (7.28). This may also be noted reaction involving oxygen displacement.

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 redox reactions 243

All alkali metals and some alkaline earth Cu>Ag. Like metals, activity series also exists
metals (Ca, Sr, and Ba) which are very good for the halogens. The power of these elements
reductants, will displace hydrogen from cold as oxidising agents decreases as we move
water. down from fluorine to iodine in group 17 of the
0 +1 –2 +1 –2 +1 0 periodic table. This implies that fluorine is so
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g) reactive that it can replace chloride, bromide
(7.33) and iodide ions in solution. In fact, fluorine is
0 +1 –2 +2 –2 +1 0 so reactive that it attacks water and displaces
Ca(s) + 2H2O(l) → Ca(OH)2 (aq) + H2(g) the oxygen of water :
(7.34) +1 –2 0 +1 –1 0

Less active metals such as magnesium and 2H2O (l) + 2F2 (g) → 4HF(aq) + O2(g) (7.40)
iron react with steam to produce dihydrogen gas: It is for this reason that the displacement
0 +1 –2 +2 –2 +1 0
reactions of chlorine, bromine and iodine
using fluorine are not generally carried out in
Mg(s) + 2H2O(l) Mg(OH)2(s) + H2(g)
aqueous solution. On the other hand, chlorine
(7.35)
can displace bromide and iodide ions in an
0 +1 –2 +3 –2 0 aqueous solution as shown below:
2Fe(s) + 3H2O(l) Fe2O3(s) + 3H2(g) (7.36) 0 +1 –1 +1 –1 0
Many metals, including those which do not Cl2 (g) + 2KBr (aq) → 2 KCl (aq) + Br2 (l)
react with cold water, are capable of displacing (7.41)
hydrogen from acids. Dihydrogen from acids 0 +1–1 +1 –1 0
may even be produced by such metals which Cl2 (g) + 2KI (aq) → 2 KCl (aq) + I2 (s)
do not react with steam. Cadmium and tin are (7.42)
the examples of such metals. A few examples As Br2 and I2 are coloured and dissolve in CCl4,
for the displacement of hydrogen from acids can easily be identified from the colour of the
are: solution. The above reactions can be written
0 +1 –1 +2 –1 0
in ionic form as:
Zn(s) + 2HCl(aq) → ZnCl2 (aq) + H2 (g) 0 –1 –1 0
(7.37) Cl2 (g) + 2Br– (aq) → 2Cl– (aq) + Br2 (l) (7.41a)
0 +1 –1 +2 –1 0 0 –1 –1 0
Mg (s) + 2HCl (aq) → MgCl2 (aq) + H2 (g) Cl2 (g) + 2I– (aq) → 2Cl– (aq) + I2 (s) (7.42b)
(7.38) Reactions (7.41) and (7.42) form the basis
0 +1 –1 +2 –1 0
of identifying Br– and I– in the laboratory
Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g) through the test popularly known as ‘Layer
(7.39)
Test’. It may not be out of place to mention
Reactions (7.37 to 7.39) are used to here that bromine likewise can displace iodide
prepare dihydrogen gas in the laboratory. ion in solution:
Here, the reactivity of metals is reflected in 0 –1 –1 0
the rate of hydrogen gas evolution, which is Br2 (l) + 2I – (aq) → 2Br– (aq) + I2 (s) (7.43)
the slowest for the least active metal Fe, and
The halogen displacement reactions have
the fastest for the most reactive metal, Mg.
a direct industrial application. The recovery
Very less active metals, which may occur in
of halogens from their halides requires an
the native state such as silver (Ag), and gold
(Au) do not react even with hydrochloric acid. oxidation process, which is represented by:
2X– → X2 + 2e– (7.44)
In section (7.2.1) we have already discussed
that the metals – zinc (Zn), copper (Cu) and here X denotes a halogen element. Whereas
silver (Ag) through tendency to lose electrons chemical means are available to oxidise Cl–,
show their reducing activity in the order Zn> Br– and I–, as fluorine is the strongest oxidising

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agent; there is no way to convert F– ions to F2 fluorine shows deviation from this behaviour
by chemical means. The only way to achieve when it reacts with alkali. The reaction that
F2 from F– is to oxidise electrolytically, the takes place in the case of fluorine is as follows:
details of which you will study at a later stage. 2 F2(g) + 2OH–(aq) → 2 F–(aq) + OF2(g) + H2O(l)
4. Disproportionation reactions (7.49)
Disproportionation reactions are a special type (It is to be noted with care that fluorine in
of redox reactions. In a disproportionation reaction (7.49) will undoubtedly attack water
reaction an element in one oxidation state to produce some oxygen also). This departure
is simultaneously oxidised and reduced. shown by fluorine is not surprising for us as
One of the r eacting substances in a we know the limitation of fluorine that, being
disproportionation reaction always contains the most electronegative element, it cannot
an element that can exist in at least three exhibit any positive oxidation state. This
oxidation states. The element in the form means that among halogens, fluorine does not
of reacting substance is in the intermediate show a disproportionation tendency.
oxidation state; and both higher and lower
oxidation states of that element are formed in Problem 7.5
the reaction. The decomposition of hydrogen Which of the following species, do not
peroxide is a familiar example of the reaction, show disproportionation reaction and
where oxygen experiences disproportionation. why ?
+1 –1 +1 –2 0 ClO–, ClO2–, ClO3– and ClO4–
2H2O2 (aq) → 2H2O(l) + O2(g) (7.45) Also write reaction for each of the species
Here the oxygen of peroxide, which is present that disproportionates.
in –1 state, is converted to zero oxidation state Solution
in O2 and decreases to –2 oxidation state in Among the oxoanions of chlorine listed
H2O. above, ClO4– does not disproportionate
Phosphorous, sulphur and chlorine because in this oxoanion chlorine is
undergo disproportionation in the alkaline present in its highest oxidation state that
medium as shown below : is, +7. The disproportionation reactions
0 –3 +1 for the other three oxoanions of chlorine
P4(s) + 3OH–(aq)+ 3H2O(l) → PH3(g) + 3H2PO2– are as follows:
(aq) +1 –1 +5
(7.46) 3ClO– → 2Cl– + ClO–3
0 –2 +2
+3 +5 –1
S8(s) + 12 OH– (aq) → 4S2– (aq) + 2S2O32–(aq) 6 ClO2– 4ClO3– + 2Cl–
+ 6H2O(l) +5 –1 +7
(7.47) 4ClO–3 → Cl– + 3 ClO4–
0 +1 –1
Cl2 (g) + 2 OH– (aq) → ClO– (aq) + Cl– (aq) + Problem 7.6
H2O (l) Suggest a scheme of classification of the
(7.48) following redox reactions
The reaction (7.48) describes the (a) N2 (g) + O2 (g) → 2 NO (g)
formation of household bleaching agents.
The hypochlorite ion (ClO –) formed in the (b) 2Pb(NO3)2(s) → 2PbO(s) + 4 NO2 (g) +
reaction oxidises the colour-bearing stains O2 (g)
of the substances to colourless compounds. (c) NaH(s) + H2O(l) → NaOH(aq) + H2 (g)
It is of interest to mention here that whereas (d) 2NO2(g) + 2OH–(aq) → NO2–(aq) +
bromine and iodine follow the same trend NO3– (aq)+H2O(l)
as exhibited by chlorine in reaction (7.48),

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Solution reaction (c), hydrogen of water has been

In reaction (a), the compound nitric displaced by hydride ion into dihydrogen
oxide is formed by the combination of gas. Therefore, this may be called as
the elemental substances, nitrogen and displacement redox reaction. The reaction
oxygen; therefore, this is an example (d) involves disproportionation of NO2
of combination redox reactions. The (+4 state) into NO2– (+3 state) and NO3–
reaction (b) involves the breaking down
(+5 state). Therefore reaction (d) is an
of lead nitrate into three components;
therefore, this is categorised under example of disproportionation redox
decomposition redox reaction. In reaction.

The Paradox of Fractional Oxidation Number

Sometimes, we come across with certain compounds in which the oxidation number of a particular
element in the compound is in fraction. Examples are:
C3O2 [where oxidation number of carbon is (4/3)],
Br3O8 [where oxidation number of bromine is (16/3)]
and Na2S4O6 (where oxidation number of sulphur is 2.5).
We know that the idea of fractional oxidation number is unconvincing to us, because electrons
are never shared/transferred in fraction. Actually this fractional oxidation state is the average
oxidation state of the element under examination and the structural parameters reveal that the
element for whom fractional oxidation state is realised is present in different oxidation states.
Structure of the species C3O2, Br3O8 and S4O62– reveal the following bonding situations:

+2 0 +2
O = C = C*= C = O
Structure of C3O2
(carbon suboxide)

Structure of Br3O8 (tribromooctaoxide) Structure of S4O62– (tetrathionate ion)

The element marked with asterisk in each species is exhibiting the different oxidation
state (oxidation number) from rest of the atoms of the same element in each of the species.
This reveals that in C3O2, two carbon atoms are present in +2 oxidation state each, whereas
the third one is present in zero oxidation state and the average is 4/3. However, the realistic
picture is +2 for two terminal carbons and zero for the middle carbon. Likewise in Br3O8, each
of the two terminal bromine atoms are present in +6 oxidation state and the middle bromine
is present in +4 oxidation state. Once again the average, that is different from reality, is
16/3. In the same fashion, in the species S4O62–, each of the two extreme sulphurs exhibits oxidation
state of +5 and the two middle sulphurs as zero. The average of four oxidation numbers of sulphurs
of the S4O62– is 2.5, whereas the reality being + 5,0,0 and +5 oxidation number respectively for
each sulphur.
We may thus, in general, conclude that the idea of fractional oxidation state should be taken
with care and the reality is revealed by the structures only. Further, whenever we come across
with fractional oxidation state of any particular element in any species, we must understand that
this is the average oxidation number only. In reality (revealed by structures only), the element in
that particular species is present in more than one whole number oxidation states. Fe3O4, Mn3O4,
Pb3O4 are some of the other examples of the compounds, which are mixed oxides, where we come
across with fractional oxidation states of the metal atom. However, the oxidation states may be in
fraction as in O2+ and O2– where it is +½ and –½ respectively.

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(a) Oxidation Number Method: In writing

Problem 7.7 equations for oxidation-reduction reactions,
Why do the following reactions proceed just as for other reactions, the compositions and
differently ? formulas must be known for the substances
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O and that react and for the products that are
formed. The oxidation number method is now
Pb3O4 + 4HNO3 → 2Pb(NO3)2 + PbO2 +
best illustrated in the following steps:
2H2O
Solution Step 1: Write the correct formula for each
reactant and product.
Pb 3 O 4 is actually a stoichiometric
Step 2: Identify atoms which undergo
mixture of 2 mol of PbO and 1 mol of
change in oxidation number in the reaction
PbO2. In PbO 2, lead is present in +4
by assigning the oxidation number to all
oxidation state, whereas the stable
elements in the reaction.
oxidation state of lead in PbO is +2. PbO2
thus can act as an oxidant (oxidising Step 3: Calculate the increase or decrease
agent) and, therefore, can oxidise Cl– ion in the oxidation number per atom and for
of HCl into chlorine. We may also keep in the entire molecule/ion in which it occurs. If
these are not equal then multiply by suitable
mind that PbO is a basic oxide. Therefore,
number so that these become equal. (If you
the reaction
realise that two substances are reduced and
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O nothing is oxidised or vice-versa, something
can be splitted into two reactions namely: is wrong. Either the formulas of reactants or
2PbO + 4HCl → 2PbCl2 + 2H2O products are wrong or the oxidation numbers
have not been assigned properly).
(acid-base reaction)
+4 –1 +2 0
Step 4: Ascertain the involvement of ions if
PbO2 + 4HCl → PbCl2 + Cl2 +2H2O the reaction is taking place in water, add H+ or
OH– ions to the expression on the appropriate
(redox reaction)
side so that the total ionic charges of reactants
Since HNO3 itself is an oxidising agent and products are equal. If the reaction is
therefore, it is unlikely that the reaction carried out in acidic solution, use H+ ions in
may occur between PbO 2 and HNO 3. the equation; if in basic solution, use OH– ions.
However, the acid-base reaction occurs Step 5 : Make the numbers of hydrogen
between PbO and HNO3 as: atoms in the expression on the two sides
2PbO + 4HNO3 → 2Pb(NO3)2 + 2H2O equal by adding water (H2O) molecules to the
It is the passive nature of PbO2 against reactants or products. Now, also check the
HNO3 that makes the reaction different number of oxygen atoms. If there are the same
from the one that follows with HCl. number of oxygen atoms in the reactants and
products, the equation then represents the
7.3.2 Balancing of Redox Reactions balanced redox reaction.
Two methods are used to balance chemical Let us now explain the steps involved in
equations for redox processes. One of these the method with the help of a few problems
methods is based on the change in the given below:
oxidation number of reducing agent and the Problem 7.8
oxidising agent and the other method is based
Write the net ionic equation for the
on splitting the redox reaction into two half
reaction of potassium dichromate(VI),
reactions — one involving oxidation and the
K2Cr2O7 with sodium sulphite, Na2SO3,
other involving reduction. Both these methods
are in use and the choice of their use rests in an acid solution to give chromium(III)
with the individual using them. ion and the sulphate ion.

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 redox reactions 247

Solution Problem 7.9

Step 1: The skeletal ionic equation is: Permanganate ion reacts with bromide
Cr2O72–(aq) + SO32–(aq) → Cr3+(aq) ion in basic medium to give manganese
dioxide and bromate ion. Write the
+ SO42–(aq)
balanced ionic equation for the reaction.
Step 2: Assign oxidation numbers for
Cr and S Solution
+6 –2 +4 –2 +3 +6 –2 Step 1: The skeletal ionic equation is :
Cr2O72–(aq) + SO32–(aq) → Cr(aq)+SO42–(aq) MnO4–(aq) + Br–(aq) → MnO2(s) + BrO3– (aq)
This indicates that the dichromate ion is Step 2: Assign oxidation numbers for
the oxidant and the sulphite ion is the Mn and Br
reductant.
+7 –1 +4 +5
Step 3: Calculate the increase and MnO4–(aq) + Br–(aq) →MnO2 (s) + BrO3– (aq)
decrease of oxidation number, and make
this indicates that permanganate ion
them equal: from step-2 we can notice
is the oxidant and bromide ion is the
that there is change in oxidation state
reductant.
of chromium and sulphur. Oxidation
state of chromium changes form +6 to Step 3: Calculate the increase and
+3. There is decrease of +3 in oxidation decrease of oxidation number, and make
state of chromium on right hand side of the increase equal to the decrease.
+7 –1 +4 +5
the equation. Oxidation state of sulphur
changes from +4 to +6. There is an increase 2MnO4–(aq)+Br–(aq) → 2MnO2(s)+BrO3–(aq)
of +2 in the oxidation state of sulphur on Step 4: As the reaction occurs in the
right hand side. To make the increase and basic medium, and the ionic charges are
decrease of oxidation state equal, place not equal on both sides, add 2 OH– ions
numeral 2 before cromium ion on right on the right to make ionic charges equal.
hand side and numeral 3 before sulphate 2MnO4– (aq) + Br– (aq) → 2MnO2(s) +
ion on right hand side and balance the BrO3–(aq) + 2OH–(aq)
chromium and sulphur atoms on both the
Step 5: Finally, count the hydrogen atoms
sides of the equation. Thus we get
and add appropriate number of water
+6 –2 +4 –2 +3 molecules (i.e. one H2O molecule) on the
Cr2O72–(aq) + 3SO32– (aq) → 2Cr3+ (aq) + left side to achieve balanced redox change.
+6 –2
2MnO4–(aq) + Br–(aq) + H2O(l) → 2MnO2(s)
3SO42– (aq)
+ BrO3– (aq) + 2OH–(aq)
Step 4: As the reaction occurs in the
acidic medium, and further the ionic (b) Half Reaction Method: In this method,
charges are not equal on both the sides, the two half equations are balanced separately
add 8H+ on the left to make ionic charges and then added together to give balanced
equal equation.
Cr2O72–(aq) + 3SO32–(aq)+ 8H+→ 2Cr3+(aq) Suppose we are to balance the equation
+ 3SO42– (aq) showing the oxidation of Fe2+ ions to Fe3+ ions
by dichromate ions (Cr2O7)2– in acidic medium,
Step 5: Finally, count the hydrogen
wherein, Cr2O72– ions are reduced to Cr3+ ions.
atoms, and add appropriate number of
The following steps are involved in this task.
water molecules (i.e., 4H2O) on the right
to achieve balanced redox change. Step 1: Produce unbalanced equation for the
reaction in ionic form :
Cr2O72– (aq) + 3SO32– (aq)+ 8H+ (aq) →
Fe2+(aq) + Cr2O72– (aq) → Fe3+ (aq) + Cr3+(aq)
2Cr3+ (aq) + 3SO42– (aq) +4H2O (l)
(7.50)

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Step 2: Separate the equation into half- Step 7: Verify that the equation contains the
reactions: same type and number of atoms and the same
+2 +3 charges on both sides of the equation. This
Oxidation half : Fe2+ (aq) → Fe3+(aq) (7.51) last check reveals that the equation is fully
+6 –2 +3 balanced with respect to number of atoms
Reduction half : Cr2O72–(aq) → Cr3+(aq) and the charges.
(7.52) For the reaction in a basic medium, first
Step 3: Balance the atoms other than O and balance the atoms as is done in acidic medium.
H in each half reaction individually. Here the Then for each H+ ion, add an equal number of
oxidation half reaction is already balanced OH– ions to both sides of the equation. Where
with respect to Fe atoms. For the reduction H+ and OH– appear on the same side of the
half reaction, we multiply the Cr3+ by 2 to equation, combine these to give H2O.
balance Cr atoms. Problem 7.10
Cr2O72–(aq) → 2 Cr3+(aq) (7.53) Permanganate(VII) ion, MnO4– in basic
Step 4: For reactions occurring in acidic solution oxidises iodide ion, I– to produce
medium, add H2O to balance O atoms and H+ molecular iodine (I2) and manganese
to balance H atoms. (IV) oxide (MnO2). Write a balanced ionic
Thus, we get : equation to represent this redox reaction.
Cr2O72– (aq) + 14H+ (aq) → 2 Cr3+(aq) + 7H2O (l) Solution
(7.54) Step 1: First we write the skeletal
Step 5: Add electrons to one side of the half ionic equation, which is
reaction to balance the charges. If need be, MnO4– (aq) + I– (aq) → MnO2(s) + I2(s)
make the number of electrons equal in the
Step 2: The two half-reactions are:
two half reactions by multiplying one or both
half reactions by appropriate number. –1 0
Oxidation half : I–(aq) → I2 (s)
The oxidation half reaction is thus +7 +4
rewritten to balance the charge: Reduction half: MnO4–(aq) → MnO2(s)
Fe2+ (aq) → Fe3+ (aq) + e– (7.55) Step 3: To balance the I atoms in the
Now in the reduction half reaction there oxidation half reaction, we rewrite it as:
are net twelve positive charges on the left hand 2I– (aq) → I2 (s)
side and only six positive charges on the right
hand side. Therefore, we add six electrons on Step 4: To balance the O atoms in the
the left side. reduction half reaction, we add two water
molecules on the right:
Cr2O72– (aq) + 14H+ (aq) + 6e– → 2Cr3+(aq) +
MnO4– (aq) → MnO2 (s) + 2 H2O (l)
7H2O (l) (7.56)
To balance the H atoms, we add four H+
To equalise the number of electrons in both ions on the left:
the half reactions, we multiply the oxidation
MnO–4 (aq) + 4 H+ (aq) → MnO2(s) + 2H2O (l)
half reaction by 6 and write as :
As the reaction takes place in a basic
6Fe2+ (aq) → 6Fe3+(aq) + 6e– (7.57)
solution, therefore, for four H+ ions, we
Step 6: We add the two half reactions to add four OH– ions to both sides of the
achieve the overall reaction and cancel the equation:
electrons on each side. This gives the net ionic MnO–4 (aq) + 4H+ (aq) + 4OH–(aq) →
equation as :
MnO2 (s) + 2 H2O(l) + 4OH– (aq)
6Fe2+(aq) + Cr2O72–(aq) + 14H+(aq) → 6 Fe3+(aq) +
Replacing the H+ and OH– ions with water,
2Cr (aq) + 7H2O(l) (7.58)
3+

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the resultant equation is: (ii) If there is no dramatic auto-colour change

(as with MnO4– titration), there are indicators
MnO4– (aq) + 2H2O (l) → MnO2 (s) + 4 OH– (aq)
which are oxidised immediately after the
Step 5 : In this step we balance the last bit of the reactant is consumed,
charges of the two half-reactions in the producing a dramatic colour change. The
manner depicted as: best example is afforded by Cr2O72–, which
2I– (aq) → I2 (s) + 2e– is not a self-indicator, but oxidises the
MnO4–(aq) + 2H2O(l) + 3e– → MnO2(s) indicator substance diphenylamine just
after the equivalence point to produce an
+ 4OH–(aq)
intense blue colour, thus signalling the
Now to equalise the number of electrons, end point.
we multiply the oxidation half-reaction by
(iii) There is yet another method which is
3 and the reduction half-reaction by 2.
interesting and quite common. Its use is
6I–(aq) → 3I2 (s) + 6e– restricted to those reagents which are able
2 MnO4– (aq) + 4H2O (l) +6e– → 2MnO2(s) to oxidise I– ions, say, for example, Cu(II):
+ 8OH– (aq) 2Cu2+(aq) + 4I–(aq) → Cu2I2(s) + I2(aq) (7.59)
Step 6: Add two half-reactions to This method relies on the facts that
obtain the net reactions after cancelling iodine itself gives an intense blue colour with
electrons on both sides. starch and has a very specific reaction with
6I –(aq) + 2MnO4–(aq) + 4H2O(l) → 3I2(s) + thiosulphate ions (S2O32–), which too is a redox
2MnO2(s) +8 OH–(aq) reaction:
Step 7: A final verification shows that I2(aq) + 2 S2O2– 3
(aq)→2I–(aq) + S4O62–(aq) (7.60)
the equation is balanced in respect of I2, though insoluble in water, remains in
the number of atoms and charges on solution containing KI as KI3.
both sides.
On addition of starch after the liberation
7.3.3 Redox Reactions as the Basis for of iodine from the reaction of Cu2+ ions on
Titrations iodide ions, an intense blue colour appears.
In acid-base systems we come across with a This colour disappears as soon as the iodine
titration method for finding out the strength is consumed by the thiosulphate ions. Thus,
of one solution against the other using a the end-point can easily be tracked and the
pH sensitive indicator. Similarly, in redox rest is the stoichiometric calculation only.
systems, the titration method can be adopted 7.3.4 Limitations of Concept of Oxidation
to determine the strength of a reductant/ Number
oxidant using a redox sensitive indicator.
The usage of indicators in redox titration is As you have observed in the above discussion,
illustrated below: the concept of redox processes has been
evolving with time. This process of evolution
(i) In one situation, the reagent itself is
is continuing. In fact, in recent past the
intensely coloured, e.g., permanganate
oxidation process is visualised as a decrease
ion, MnO4–. Here MnO4– acts as the self
in electron density and reduction process as
indicator. The visible end point in this case
is achieved after the last of the reductant an increase in electron density around the
(Fe2+ or C2O42–) is oxidised and the first atom(s) involved in the reaction.
lasting tinge of pink colour appears at 7.4 Redox Reactions and Electrode
MnO4– concentration as low as 10–6 mol dm–3
Processes
(10–6 mol L–1). This ensures a minimal
‘overshoot’ in colour beyond the equivalence The experiment corresponding to reaction
point, the point where the reductant and (7.15), can also be observed if zinc rod is
the oxidant are equal in terms of their dipped in copper sulphate solution. The
mole stoichiometry. redox reaction takes place and during the

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reaction, zinc is oxidised to zinc ions and are represented as Zn2+/Zn and Cu2+/Cu.
copper ions are reduced to metallic copper In both cases, oxidised form is put before
due to direct transfer of electrons from zinc the reduced form. Now we put the beaker
to copper ion. During this reaction heat is containing copper sulphate solution and the
also evolved. Now we modify the experiment beaker containing zinc sulphate solution
in such a manner that for the same redox side by side (Fig. 7.3). We connect solutions
reaction transfer of electrons takes place in two beakers by a salt bridge (a U-tube
indirectly. This necessitates the separation containing a solution of potassium chloride
of zinc metal from copper sulphate solution. or ammonium nitrate usually solidified by
We take copper sulphate solution in a beaker boiling with agar agar and later cooling to a
and put a copper strip or rod in it. We also jelly like substance). This provides an electric
take zinc sulphate solution in another beaker contact between the two solutions without
and put a zinc rod or strip in it. Now reaction allowing them to mix with each other. The
takes place in either of the beakers and at the zinc and copper rods are connected by a
interface of the metal and its salt solution in metallic wire with a provision for an ammeter
each beaker both the reduced and oxidized and a switch. The set-up as shown in Fig.7.3
forms of the same species are present. These is known as Daniell cell. When the switch is
represent the species in the reduction and in the off position, no reaction takes place in
oxidation half reactions. A redox couple is either of the beakers and no current flows
defined as having together the oxidised and through the metallic wire. As soon as the
reduced forms of a substance taking part in switch is in the on position, we make the
an oxidation or reduction half reaction. following observations:
This is represented by separating the 1. The transfer of electrons now does not
oxidised form from the reduced form by take place directly from Zn to Cu2+ but
a vertical line or a slash representing an through the metallic wire connecting the
interface (e.g. solid/solution). For example two rods as is apparent from the arrow
in this experiment the two redox couples which indicates the flow of current.
2. The electricity from solution in one beaker
to solution in the other beaker flows by
the migration of ions through the salt
bridge. We know that the flow of current
is possible only if there is a potential
difference between the copper and zinc
rods known as electrodes here.
The potential associated with each
electrode is known as electrode potential.
If the concentration of each species taking
part in the electrode reaction is unity (if any
gas appears in the electrode reaction, it is
confined to 1 atmospheric pressure) and
further the reaction is carried out at 298K,
then the potential of each electrode is said
Fig.7.3 The set-up for Daniell cell. Electrons to be the Standard Electrode Potential. By
produced at the anode due to oxidation convention, the standard electrode potential
of Zn travel through the external circuit (E) of hydrogen electrode is 0.00 volts. The
to the cathode where these reduce the
electrode potential value for each electrode
copper ions. The circuit is completed
inside the cell by the migration of ions process is a measure of the relative tendency
through the salt bridge. It may be noted of the active species in the process to remain
that the direction of current is opposite to in the oxidised/reduced form. A negative E
the direction of electron flow. means that the redox couple is a stronger

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 redox reactions 251

reducing agent than the H+/H2 couple. A information from them. The values of standard
positive E means that the redox couple is a electrode potentials for some selected electrode
weaker reducing agent than the H+/H2 couple. processes (reduction reactions) are given in
The standard electrode potentials are very Table 7.1. You will learn more about electrode
important and we can get a lot of other useful reactions and cells in Class XII.
Table 7.1 The Standard Electrode Potentials at 298 K
Ions are present as aqueous species and H2O as liquid; gases and
solids are shown by g and s respectively.
Reaction (Oxidised form + ne– → Reduced form) E / V

F2(g) + 2e– → 2F– 2.87

Co 3+
+e –
→ Co2+ 1.81
H2O2 + 2H+ + 2e– → 2H2O 1.78
MnO4– + 8H+ + 5e– → Mn + 4H2O
2+
1.51
Au3+ + 3e– → Au(s) 1.40
Cl2(g) + 2e– → 2Cl– 1.36
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O 1.33
O2(g) + 4H+ + 4e– → 2H2O 1.23
MnO2(s) + 4H+ + 2e– → Mn2+ + 2H2O 1.23
Br2 + 2e– → 2Br– 1.09
NO3– + 4H+ + 3e– → NO(g) + 2H2O 0.97

Increasing strength of reducing agent

Increasing strength of oxidising agent

2Hg2+ + 2e– → Hg2

2+
0.92
Ag+ + e– → Ag(s) 0.80
Fe3+ + e– → Fe 0.77
2+

O2(g) + 2H+ + 2e– → H2O2 0.68

I2(s) + 2e– → 2I– 0.54
Cu+ + e– → Cu(s) 0.52
Cu2+ + 2e– → Cu(s) 0.34
AgCl(s) + e– → Ag(s) + Cl
–
0.22
AgBr(s) + e– → Ag(s) + Br– 0.10
2H+ + 2e– → H2(g) 0.00
Pb2+ + 2e– → Pb(s) –0.13
Sn2+ + 2e– → Sn(s) –0.14
Ni2+ + 2e– → Ni(s) –0.25
Fe2+ + 2e– → Fe(s) –0.44
Cr3+ + 3e– → Cr(s) –0.74
Zn2+ + 2e– → Zn(s) –0.76
2H2O + 2e– → H2(g) + 2OH– –0.83
Al3+
+ 3e –
→ Al(s) –1.66
Mg2+ + 2e– → Mg(s) –2.36
Na + e+ –
→ Na(s) –2.71
Ca2+ + 2e– → Ca(s) –2.87
K +e
+ –
→ K(s) –2.93
Li+ + e– → Li(s) –3.05

1. A negative E means that the redox couple is a stronger reducing agent than the H+/H2 couple.
2. A positive E means that the redox couple is a weaker reducing agent than the H+/H2 couple.

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 252 chemistry

SUMMARY

Redox reactions form an important class of reactions in which oxidation and reduction
occur simultaneously. Three tier conceptualisation viz, classical, electronic and oxidation
number, which is usually available in the texts, has been presented in detail. Oxidation,
reduction, oxidising agent (oxidant) and reducing agent (reductant) have been viewed
according to each conceptualisation. Oxidation numbers are assigned in accordance with a
consistent set of rules. Oxidation number and ion-electron method both are useful means in
writing equations for the redox reactions. Redox reactions are classified into four categories:
combination, decomposition displacement and disproportionation reactions. The concept of
redox couple and electrode processes is introduced here. The redox reactions find wide
applications in the study of electrode processes and cells.

EXERCISES

7.1 Assign oxidation number to the underlined elements in each of the following species:
(a) NaH2PO4 (b) NaHSO4 (c) H4P2O7 (d) K2MnO4
(e) CaO2 (f) NaBH4 (g) H2S2O7 (h) KAl(SO4)2.12 H2O
7.2 What are the oxidation number of the underlined elements in each of the following
and how do you rationalise your results ?
(a) KI3 (b) H2S4O6 (c) Fe3O4 (d) CH3CH2OH (e) CH3COOH
7.3 Justify that the following reactions are redox reactions:
(a) CuO(s) + H2(g) → Cu(s) + H2O(g)
(b) Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
(c) 4BCl3(g) + 3LiAlH4(s) → 2B2H6(g) + 3LiCl(s) + 3 AlCl3 (s)
(d) 2K(s) + F2(g) → 2K+F– (s)
(e) 4 NH3(g) + 5 O2(g) → 4NO(g) + 6H2O(g)
7.4 Fluorine reacts with ice and results in the change:
H2O(s) + F2(g) → HF(g) + HOF(g)
Justify that this reaction is a redox reaction.
7.5 Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5, Cr2O72–
and NO3–. Suggest structure of these compounds. Count for the fallacy.
7.6 Write formulas for the following compounds:
(a) Mercury(II) chloride (b) Nickel(II) sulphate
(c) Tin(IV) oxide (d) Thallium(I) sulphate
(e) Iron(III) sulphate ( f ) Chromium(III) oxide
7.7 Suggest a list of the substances where carbon can exhibit oxidation states from –4
to +4 and nitrogen from –3 to +5.
7.8 While sulphur dioxide and hydrogen peroxide can act as oxidising as well as reducing
agents in their reactions, ozone and nitric acid act only as oxidants. Why ?
7.9 Consider the reactions:
(a) 6 CO2(g) + 6H2O(l) → C6 H12 O6(aq) + 6O2(g)

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 redox reactions 253

(b) O3(g) + H2O2(l) → H2O(l) + 2O2(g)

Why it is more appropriate to write these reactions as :
(a) 6CO2(g) + 12H2O(l) → C6 H12 O6(aq) + 6H2O(l) + 6O2(g)
(b) O3(g) + H2O2 (l) → H2O(l) + O2(g) + O2(g)
Also suggest a technique to investigate the path of the above (a) and (b) redox
reactions.
7.10 The compound AgF2 is unstable compound. However, if formed, the compound acts
as a very strong oxidising agent. Why ?
7.11 Whenever a reaction between an oxidising agent and a reducing agent is carried out,
a compound of lower oxidation state is formed if the reducing agent is in excess and
a compound of higher oxidation state is formed if the oxidising agent is in excess.
Justify this statement giving three illustrations.
7.12 How do you count for the following observations ?
(a) Though alkaline potassium permanganate and acidic potassium permanganate
both are used as oxidants, yet in the manufacture of benzoic acid from toluene
we use alcoholic potassium permanganate as an oxidant. Why ? Write a balanced
redox equation for the reaction.
(b) When concentrated sulphuric acid is added to an inorganic mixture containing
chloride, we get colourless pungent smelling gas HCl, but if the mixture contains
bromide then we get red vapour of bromine. Why ?
7.13 Identify the substance oxidised reduced, oxidising agent and reducing agent for
each of the following reactions:
(a) 2AgBr (s) + C6H6O2(aq) → 2Ag(s) + 2HBr (aq) + C6H4O2(aq)
(b) HCHO(l) + 2[Ag (NH3)2]+(aq) + 3OH–(aq) → 2Ag(s) + HCOO–(aq) + 4NH3(aq)
+ 2H2O(l)
(c) HCHO (l) + 2 Cu2+(aq) + 5 OH–(aq) → Cu2O(s) + HCOO–(aq) + 3H2O(l)
(d) N2H4(l) + 2H2O2(l) → N2(g) + 4H2O(l)
(e) Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
7.14 Consider the reactions :
2 S2O32– (aq) + I2(s) → S4 O62–(aq) + 2I–(aq)
S2O32–(aq) + 2Br2(l) + 5 H2O(l) → 2SO42–(aq) + 4Br–(aq) + 10H+(aq)
Why does the same reductant, thiosulphate react differently with iodine and
bromine ?
7.15 Justify giving reactions that among halogens, fluorine is the best oxidant and among
hydrohalic compounds, hydroiodic acid is the best reductant.
7.16 Why does the following reaction occur ?
XeO64– (aq) + 2F (aq) + 6H+(aq) → XeO3(g)+ F2(g) + 3H2O(l)
–

What conclusion about the compound Na4XeO6 (of which XeO4–

6
is a part) can be
drawn from the reaction.
7.17 Consider the reactions:
(a) H3PO2(aq) + 4 AgNO3(aq) + 2 H2O(l) → H3PO4(aq) + 4Ag(s) + 4HNO3(aq)
(b) H3PO2(aq) + 2CuSO4(aq) + 2 H2O(l) → H3PO4(aq) + 2Cu(s) + H2SO4(aq)
(c) C6H5CHO(l) + 2[Ag (NH3)2]+(aq) + 3OH–(aq) → C6H5COO–(aq) + 2Ag(s) +
4NH3 (aq) + 2 H2O(l)
(d) C6H5CHO(l) + 2Cu (aq) + 5OH (aq) → No change observed.
2+ –

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 254 chemistry

What inference do you draw about the behaviour of Ag+ and Cu2+ from these
reactions ?
7.18 Balance the following redox reactions by ion – electron method :
(a) MnO4– (aq) + I– (aq) → MnO2 (s) + I2(s) (in basic medium)
(b) MnO4– (aq) + SO2 (g) → Mn2+ (aq) + HSO4– (aq) (in acidic solution)
(c) H2O2 (aq) + Fe2+ (aq) → Fe3+ (aq) + H2O (l) (in acidic solution)
(d) Cr2O72– + SO2(g) → Cr3+ (aq) + SO42– (aq) (in acidic solution)
7.19 Balance the following equations in basic medium by ion-electron method and
oxidation number methods and identify the oxidising agent and the reducing agent.
(a) P4(s) + OH–(aq) → PH3(g) + HPO2– (aq)
(b) N2H4(l) + ClO3–(aq) → NO(g) + Cl–(g)
(c) Cl2O7 (g) + H2O2(aq) → ClO2–(aq) + O2(g) + H+
7.20 What sorts of informations can you draw from the following reaction ?
(CN)2(g) + 2OH–(aq) → CN–(aq) + CNO–(aq) + H2O(l)
7.21 The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+,
MnO2, and H+ ion. Write a balanced ionic equation for the reaction.
7.22 Consider the elements :
Cs, Ne, I and F
(a) Identify the element that exhibits only negative oxidation state.
(b) Identify the element that exhibits only postive oxidation state.
(c) Identify the element that exhibits both positive and negative oxidation states.
(d) Identify the element which exhibits neither the negative nor does the positive
oxidation state.
7.23 Chlorine is used to purify drinking water. Excess of chlorine is harmful. The excess
of chlorine is removed by treating with sulphur dioxide. Present a balanced equation
for this redox change taking place in water.
7.24 Refer to the periodic table given in your book and now answer the following questions:
(a) Select the possible non metals that can show disproportionation reaction.
(b) Select three metals that can show disproportionation reaction.
7.25 In Ostwald’s process for the manufacture of nitric acid, the first step involves the
oxidation of ammonia gas by oxygen gas to give nitric oxide gas and steam. What is
the maximum weight of nitric oxide that can be obtained starting only with 10.00
g. of ammonia and 20.00 g of oxygen ?
7.26 Using the standard electrode potentials given in the Table 8.1, predict if the reaction
between the following is feasible:
(a) Fe3+(aq) and I–(aq)
(b) Ag+(aq) and Cu(s)
(c) Fe3+ (aq) and Cu(s)
(d) Ag(s) and Fe3+(aq)
(e) Br2(aq) and Fe2+(aq).

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 redox reactions 255

7.27 Predict the products of electrolysis in each of the following:

(i) An aqueous solution of AgNO3 with silver electrodes
(ii) An aqueous solution AgNO3 with platinum electrodes
(iii) A dilute solution of H2SO4 with platinum electrodes
(iv) An aqueous solution of CuCl2 with platinum electrodes.
7.28 Arrange the following metals in the order in which they displace each other from
the solution of their salts.
Al, Cu, Fe, Mg and Zn.
7.29 Given the standard electrode potentials,
K+/K = –2.93V, Ag+/Ag = 0.80V,
Hg2+/Hg = 0.79V
Mg2+/Mg = –2.37V. Cr3+/Cr = –0.74V
arrange these metals in their increasing order of reducing power.
7.30 Depict the galvanic cell in which the reaction Zn(s) + 2Ag+(aq) → Zn2+(aq) +2Ag(s)
takes place, Further show:
(i) which of the electrode is negatively charged,
(ii) the carriers of the current in the cell, and
(iii) individual reaction at each electrode.

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 256 chemistry

Unit 8

Organic Chemistry – Some Basic

Principles and Techniques

In the previous unit you have learnt that the element

carbon has the unique property called catenation due to
which it forms covalent bonds with other carbon atoms.
After studying this unit, you will It also forms covalent bonds with atoms of other elements
be able to
like hydrogen, oxygen, nitrogen, sulphur, phosphorus
• understand reasons for and halogens. The resulting compounds are studied
tetravalence of carbon and under a separate branch of chemistry called organic
shapes of organic molecules; chemistry. This unit incorporates some basic principles
• write structures of organic and techniques of analysis required for understanding the
molecules in various ways; formation and properties of organic compounds.
• classify the organic compounds;
• name the compounds according
8.1 General Introduction
to IUPAC system of nomenclature
and also derive their structures Organic compounds are vital for sustaining life on earth
from the given names; and include complex molecules like genetic information
• understand the concept of bearing deoxyribonucleic acid (DNA) and proteins that
organic reaction mechanism; constitute essential compounds of our blood, muscles and
• explain the influence of electronic skin. Organic compounds appear in materials like clothing,
displacements on structure and fuels, polymers, dyes and medicines. These are some of
reactivity of organic compounds; the important areas of application of these compounds.
• recognise the types of organic Science of organic chemistry is about two hundred
reactions; years old. Around the year 1780, chemists began to
• learn the techniques of distinguish between organic compounds obtained from
purification of organic plants and animals and inorganic compounds prepared
compounds;
from mineral sources. Berzilius, a Swedish chemist
• write the chemical reactions
proposed that a ‘vital force’ was responsible for the
involved in the qualitative
formation of organic compounds. However, this notion
analysis of organic compounds;
was rejected in 1828 when F. Wohler synthesised an
• understand the principles
involved in quantitative analysis
organic compound, urea from an inorganic compound,
of organic compounds. ammonium cyanate.
NH4CNO NH2CONH2
Ammonium cyanate Urea
The pioneering synthesis of acetic acid by Kolbe
(1845) and that of methane by Berthelot (1856) showed
conclusively that organic compounds could be synthesised
from inorganic sources in a laboratory.

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 organic chemistry – some basic principles and techniques 257

The development of electronic theory of Thus, in H2C=CH2 molecule all the atoms
covalent bonding ushered organic chemistry must be in the same plane. The p orbitals are
into its modern shape. mutually parallel and both the p orbitals are
perpendicular to the plane of the molecule.
8.2 TETRAVALENCE OF CARBON:
Rotation of one CH2 fragment with respect
SHAPES OF ORGANIC COMPOUNDS
to other interferes with maximum overlap
8.2.1 The Shapes of Carbon Compounds of p orbitals and, therefore, such rotation
The knowledge of fundamental concepts of about carbon-carbon double bond (C=C) is
molecular structure helps in understanding restricted. The electron charge cloud of the π
and predicting the properties of organic bond is located above and below the plane of
compounds. You have already learnt theories bonding atoms. This results in the electrons
of valency and molecular structure in Unit 4. being easily available to the attacking
Also, you already know that tetravalence of reagents. In general, π bonds provide the most
carbon and the formation of covalent bonds reactive centres in the molecules containing
by it are explained in terms of its electronic multiple bonds.
configuration and the hybridisation of s and p
orbitals. It may be recalled that formation and
Problem 8.1
the shapes of molecules like methane (CH4),
ethene (C2H4), ethyne (C2H2) are explained How many σ and π bonds are present in
in terms of the use of sp3, sp2 and sp hybrid each of the following molecules?
orbitals by carbon atoms in the respective (a) HC≡CCH=CHCH3 (b) CH2=C=CHCH3
molecules.
Solution
Hybridisation influences the bond length
and bond enthalpy (strength) in compounds. (a) σC – C: 4; σC–H : 6; πC=C :1; π C≡C:2
The sp hybrid orbital contains more s (b) σC – C: 3; σC–H: 6; πC=C: 2.
character and hence it is closer to its nucleus
and forms shorter and stronger bonds than Problem 8.2
the sp3 hybrid orbital. The sp2 hybrid orbital What is the type of hybridisation of each
is intermediate in s character between sp carbon in the following compounds?
and sp3 and, hence, the length and enthalpy
of the bonds it forms, are also intermediate (a) CH3Cl, (b) (CH3)2CO, (c) CH3CN,
between them. The change in hybridisation (d) HCONH2, (e) CH3CH=CHCN
affects the electronegativity of carbon. The
Solution
greater the s character of the hybrid orbitals,
the greater is the electronegativity. Thus, a (a) sp3, (b) sp3, sp2, (c) sp3, sp, (d) sp2, (e)
carbon atom having an sp hybrid orbital with sp3, sp2, sp2, sp
50% s character is more electronegative than Problem 8.3
that possessing sp2 or sp3 hybridised orbitals.
This relative electronegativity is reflected in Write the state of hybridisation of carbon
several physical and chemical properties of in the following compounds and shapes
the molecules concerned, about which you of each of the molecules.
will learn in later units. (a) H2C=O, (b) CH3F, (c) HC≡N.
8.2.2 Some Characteristic Features of π Solution
Bonds
(a) sp2 hybridised carbon, trigonal planar;
In a π (pi) bond formation, parallel orientation (b) sp3 hybridised carbon, tetrahedral; (c)
of the two p orbitals on adjacent atoms is sp hybridised carbon, linear.
necessary for a proper sideways overlap.

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 258 chemistry

8.3 STRUCTURAL RepresenTATIONS Similarly, CH3CH2CH2CH2CH2CH2CH2CH3

OF organic COMPOUNDs can be further condensed to CH3(CH2)6CH3.
8.3.1 Complete, Condensed and Bond-line For further simplification, organic chemists
Structural Formulas use another way of r epr esenting the
structures, in which only lines are used.
Structures of organic compounds are
In this bond-line structural representation
represented in several ways. The Lewis
of organic compounds, carbon and
structure or dot structure, dash structure,
hydrogen atoms are not shown and the
condensed structure and bond line structural
lines representing carbon-carbon bonds are
formulas are some of the specific types. The
drawn in a zig-zag fashion. The only atoms
Lewis structures, however, can be simplified
specifically written are oxygen, chlorine,
by representing the two-electron covalent
nitrogen etc. The terminals denote methyl
bond by a dash (–). Such a structural formula
(–CH3) groups (unless indicated otherwise by
focuses on the electrons involved in bond
a functional group), while the line junctions
formation. A single dash represents a single
denote carbon atoms bonded to appropriate
bond, double dash is used for double bond
number of hydrogens required to satisfy the
and a triple dash represents triple bond. Lone-
valency of the carbon atoms. Some of the
pairs of electrons on heteroatoms (e.g., oxygen,
examples are represented as follows:
nitrogen, sulphur, halogens etc.) may or may
not be shown. Thus, ethane (C2H6), ethene (i) 3-Methyloctane can be represented in
(C2H4), ethyne (C2H2) and methanol (CH3OH) various forms as:
can be represented by the following structural (a) CH3CH2CHCH2CH2CH2CH2CH3
formulas. Such structural representations are |
called complete structural formulas. CH3

(b)

Ethane Ethene

(c)

Ethyne Methanol

These structural formulas can be further

abbreviated by omitting some or all of the
dashes representing covalent bonds and by
(ii) Various ways of representing 2-bromo
indicating the number of identical groups
butane are:
attached to an atom by a subscript. The
resulting expression of the compound is
called a condensed structural formula. Thus,
(a) CH3CHBrCH2CH3 (b)
ethane, ethene, ethyne and methanol can be
written as:
CH3CH3 H2C=CH2 HC≡CH CH3OH
(c)
Ethane Ethene Ethyne Methanol

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 organic chemistry – some basic principles and techniques 259

In cyclic compounds, the bond-line formulas

may be given as follows:
(b)
Solution
Condensed formula:
Cyclopropane (a) HO(CH2)3CH(CH3)CH(CH3)2
(b) HOCH(CN)2
Bond-line formula:
(a)

Cyclopentane

(b)

chlorocyclohexane

Problem 8.6
Problem 8.4
Expand each of the following bond-line
Expand each of the following condensed formulas to show all the atoms including
formulas into their complete structural carbon and hydrogen
formulas. (a)
(a) CH3CH2COCH2CH3
(b) CH3CH=CH(CH2)3CH3

Solution (b)

(a)
(c)

(b) (d)

Solution
Problem 8.5
For each of the following compounds,
write a condensed formula and also their
bond-line formula.

(a) HOCH2CH2CH2CH(CH3)CH(CH3)CH3

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 260 chemistry

Molecular Models
Molecular models are physical devices
that are used for a better visualisation and
perception of three-dimensional shapes
of organic molecules. These are made of
wood, plastic or metal and are commercially
available. Commonly three types of molecular
models are used: (1) Framework model, (2)
Ball-and-stick model, and (3) Space filling
model. In the framework model only the
bonds connecting the atoms of a molecule
and not the atoms themselves are shown.
This model emphasizes the pattern of
bonds of a molecule while ignoring the size
of atoms. In the ball-and-stick model, both
the atoms and the bonds are shown. Balls
represent atoms and the stick denotes a
bond. Compounds containing C=C (e.g.,
ethene) can best be represented by using
8.3.2 Three-Dimensional
springs in place of sticks. These models are
Representation of Organic referred to as ball-and-spring model. The
Molecules space-filling model emphasises the relative
The three-dimensional (3-D) structure of size of each atom based on its van der Waals
organic molecules can be represented on radius. Bonds are not shown in this model.
paper by using certain conventions. For It conveys the volume occupied by each atom
example, by using solid ( ) and dashed in the molecule. In addition to these models,
computer graphics can also be used for
( ) wedge formula, the 3-D image of a
molecular modelling.
molecule from a two-dimensional picture
can be perceived. In these formulas the
solid-wedge is used to indicate a bond
projecting out of the plane of paper, towards
the observer. The dashed-wedge is used to
depict the bond projecting out of the plane of
the paper and away from the observer. Wedges
are shown in such a way that the broad end of
the wedge is towards the observer. The bonds Framework model Ball and stick model
lying in plane of the paper are depicted by
using a normal line (—). 3-D representation of
methane molecule on paper has been shown
in Fig. 8.1

Space filling model

Fig. 8.2
Fig. 8.1 Wedge-and-dash representation of CH4

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 organic chemistry – some basic principles and techniques 261

8.4 Classification of Organic (homocyclic).

Compounds
The existing large number of organic
compounds and their ever -increasing
numbers has made it necessary to classify
them on the basis of their structures. Organic Cyclopropane Cyclohexene Cyclohexane
compounds are broadly classified as follows:
Sometimes atoms other than carbon are
also present in the ring (heterocylic).
Tetrahydrofuran given below is an example
of this type of compound:

Tetrahydrofuran
These exhibit some of the properties similar
to those of aliphatic compounds.
(b) Aromatic compounds
Aromatic compounds are special types of
compounds. You will learn about these
compounds in detail in Unit 9. These include
benzene and other related ring compounds
(benzenoid). Like alicyclic compounds,
aromatic comounds may also have hetero
atom in the ring. Such compounds are called
I. Acyclic or open chain compounds hetrocyclic aromatic compounds. Some of
the examples of various types of aromatic
These compounds are also called as aliphatic
compounds are:
compounds and consist of straight or
branched chain compounds, for example: Benzenoid aromatic compounds

CH3CH3
Ethane

Isobutane
Benzene Aniline Naphthalene
Non-benzenoid compound

Acetaldehyde Acetic acid

II C y c l i c o r c l o s e d c h a i n o r r i n g
compounds
(a) Alicyclic compounds Tropone
Alicyclic (aliphatic cyclic) compounds contain
carbon atoms joined in the form of a ring

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 262 chemistry

Heterocyclic aromatic compounds so because it is found in citrus fruits and the

acid found in red ant is named formic acid
since the Latin word for ant is formica. These
names are traditional and are considered
as trivial or common names. Some common
Furan Thiophene Pyridine names are followed even today. For example,
Organic compounds can also be classified Buckminsterfullerene is a common name
on the basis of functional groups, into families given to the newly discovered C60 cluster (a
or homologous series. form of carbon) noting its structural similarity
8.4.1 Functional Group to the geodesic domes popularised by the
famous architect R. Buckminster Fuller.
The functional group is an atom or a group Common names are useful and in many
of atoms joined to the carbon chain which is cases indispensable, particularly when the
responsible for the characteristic chemical alternative systematic names are lengthy and
properties of the organic compounds. The complicated. Common names of some organic
examples are hydroxyl group (–OH), aldehyde compounds are given in Table 8.1.
group (–CHO) and carboxylic acid group (–
COOH) etc. Table 8.1 Common or Trivial Names of Some
Organic Compounds
8.4.2 Homologous Series
A group or a series of organic compounds each
containing a characteristic functional group
forms a homologous series and the members of
the series are called homologues. The members
of a homologous series can be represented by
general molecular formula and the successive
members differ from each other in molecular
formula by a –Ch2 unit. There are a number
of homologous series of organic compounds.
Some of these are alkanes, alkenes, alkynes,
haloalkanes, alkanols, alkanals, alkanones,
alkanoic acids, amines etc.
It is also possible that a compound contains
two or more identical or different functional
groups. This gives rise to polyfunctional
compounds.
8.5 NOMENCLATURE OF ORGANIC
COMPOUNDS
Organic chemistry deals with millions of 8.5.1 The IUPAC System of Nomenclature
compounds. In order to clearly identify
A systematic name of an organic compound
them, a systematic method of naming has
is generally derived by identifying the parent
been developed and is known as the IUPAC
hydrocarbon and the functional group(s)
(International Union of Pure and Applied
attached to it. See the example given below.
Chemistry) system of nomenclature. In this
systematic nomenclature, the names are
correlated with the structure such that the
reader or listener can deduce the structure
from the name.
Before the IUPAC system of nomenclature,
however, organic compounds were assigned
names based on their origin or certain
properties. For instance, citric acid is named

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 organic chemistry – some basic principles and techniques 263

By further using prefixes and suffixes, the In order to name such compounds, the names
parent name can be modified to obtain the of alkyl groups are prefixed to the name of
actual name. Compounds containing carbon parent alkane. An alkyl group is derived
and hydrogen only are called hydrocarbons. from a saturated hydrocarbon by removing
A hydrocarbon is termed saturated if it a hydrogen atom from carbon. Thus, CH4
contains only carbon-carbon single bonds. becomes -CH3 and is called methyl group. An
The IUPAC name for a homologous series of alkyl group is named by substituting ‘yl’ for
such compounds is alkane. Paraffin (Latin: ‘ane’ in the corresponding alkane. Some alkyl
little affinity) was the earlier name given to groups are listed in Table 8.3.
these compounds. Unsaturated hydrocarbons Table 8.3 Some Alkyl Groups
are those, which contain at least one carbon-
carbon double or triple bond.
8.5.2 IUPAC Nomenclature of Alkanes
Straight chain hydrocarbons: The names
of such compounds are based on their chain
structure, and end with suffix ‘-ane’ and carry
a prefix indicating the number of carbon
atoms present in the chain (except from CH4
to C4H10, where the prefixes are derived from
trivial names). The IUPAC names of some
straight chain saturated hydrocarbons are
Abbreviations are used for some alkyl
given in Table 8.2. The alkanes in Table
groups. For example, methyl is abbreviated as
8.2 differ from each other by merely the
Me, ethyl as Et, propyl as Pr and butyl as Bu.
number of -CH2 groups in the chain. They are
The alkyl groups can be branched also. Thus,
homologues of alkane series.
propyl and butyl groups can have branched
Table 8.2 IUPAC Names of Some Unbranched structures as shown below.
Saturated Hydrocarbons CH3-CH- CH3-CH2-CH- CH3-CH-CH2-
  
CH3 CH3 CH3
Isopropyl- sec-Butyl- Isobutyl-
CH3 CH3
 
CH3-C- CH3-C-CH2-
 
CH3 CH3
tert-Butyl- Neopentyl-
Branched chain hydrocarbons: In a Common branched groups have specific
branched chain compound small chains of trivial names. For example, the propyl groups
carbon atoms are attached at one or more can either be n-propyl group or isopropyl
carbon atoms of the parent chain. The small group. The branched butyl groups are called
carbon chains (branches) are called alkyl sec-butyl, isobutyl and tert-butyl group.
groups. For example: We also encounter the structural unit,
–CH2C(CH3)3, which is called neopentyl group.
CH3–CH–CH2–CH3 CH3–CH–CH2–CH–CH3
   Nomenclature of branched chain alkanes:
CH3 CH2CH3 CH3 We encounter a number of branched chain
alkanes. The rules for naming them are given
(a)(b) below.

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1. First of all, the longest carbon chain in separated from the groups by hyphens
the molecule is identified. In the example and there is no break between methyl
(I) given below, the longest chain has nine and nonane.]
carbons and it is considered as the parent 4. If two or more identical substituent
or root chain. Selection of parent chain as groups are present then the numbers
shown in (II) is not correct because it has are separated by commas. The names of
only eight carbons. identical substituents are not repeated,
instead prefixes such as di (for 2), tri
(for 3), tetra (for 4), penta (for 5), hexa (for
6) etc. are used. While writing the name
of the substituents in alphabetical order,
these prefixes, however, are not considered.
Thus, the following compounds are
named as:
CH3 CH3 CH3 CH3
    
CH3-CH-CH2-CH-CH3 CH3 C CH2CH CH3
1 2 3 4 5 1 2 3 4 5
2,4-Dimethylpentane 2,2,4-Trimethylpentane
2. The carbon atoms of the parent chain are
numbered to identify the parent alkane H3C H2C CH3
and to locate the positions of the carbon  
atoms at which branching takes place due CH3CH2CHCCH2CH2CH3
to the substitution of alkyl group in place 1 2 3 4 5 6 7
of hydrogen atoms. The numbering is CH3
done in such a way that the branched 3-Ethyl-4,4-dimethylheptane
carbon atoms get the lowest possible
numbers. Thus, the numbering in the 5. If the two substituents are found in
above example should be from left to right equivalent positions, the lower number
(branching at carbon atoms 2 and 6) and is given to the one coming first in the
not from right to left (giving numbers alphabetical listing. Thus, the following
4 and 8 to the carbon atoms at which compound is 3-ethyl-6-methyloctane and
branches are attached). not 6-ethyl-3-methyloctane.
1 2 3 4 5 6 7 8 9
CCCCCCCCC 1 2 3 4 5 6 7 8
  CH3 — CH2—CH—CH2—CH2—CH—CH2 —CH3
C CC  
CH2CH3 CH3
9 8 7 6 5 4 3 2 1
CCCCCCCCC 6. The branched alkyl groups can be
  named by following the above mentioned
C CC procedures. However, the carbon atom
3. The names of alkyl groups attached of the branch that attaches to the root
as a branch are then prefixed to the alkane is numbered 1 as exemplified
name of the parent alkane and position below.
of the substituents is indicated by the
4 3 2 1
appropriate numbers. If different alkyl
CH3–CH–CH2–CH–
groups are present, they are listed in
alphabetical order. Thus, name for the  
compound shown above is: 6-ethyl-2- CH3 CH3
1,3-Dimethylbutyl-
methylnonane. [Note: the numbers are

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 organic chemistry – some basic principles and techniques 265

The name of such branched chain alkyl group Cyclic Compounds: A saturated monocyclic
is placed in parenthesis while naming the compound is named by prefixing ‘cyclo’ to the
compound. While writing the trivial names corresponding straight chain alkane. If side
of substituents’ in alphabetical order, the chains are present, then the rules given above
prefixes iso- and neo- are considered to be are applied. Names of some cyclic compounds
the part of the fundamental name of alkyl are given below.
group. The prefixes sec- and tert- are not
considered to be the part of the fundamental
name. The use of iso and related common
prefixes for naming alkyl groups is also
allowed by the IUPAC nomenclature as long
as these are not further substituted. In multi-
substituted compounds, the following rules
may aso be remembered:
• If there happens to be two chains of equal
size, then that chain is to be selected which
contains more number of side chains.
3-Ethyl-1,1-dimethylcyclohexane
• After selection of the chain, numbering (not 1-ethyl-3,3-dimethylcyclohexane)
is to be done from the end closer to the
substituent. Problem 8.7
Structures and IUPAC names of some
hydrocarbons are given below. Explain
why the names given in the parentheses
are incorrect.

2,5,6- Trimethyloctane
[and not 3,4,7-Trimethyloctane]

5-(2-Ethylbutyl)-3,3-dimethyldecane
[and not 5-(2,2-Dimethylbutyl)-3-ethyldecane]

3-Ethyl-5-methylheptane
[and not 5-Ethyl-3-methylheptane]

Solution
(a) Lowest locant number, 2,5,6 is
lower than 3,5,7, (b) substituents are
5-sec-Butyl-4-isopropyldecane in equivalent position; lower number is
given to the one that comes first in the
name according to alphabetical order.

8.5.3 Nomenclature of Organic

Compounds having Functional
Group(s)
A functional group, as defined earlier, is an
atom or a group of atoms bonded together in
5-(2,2-Dimethylpropyl)nonane a unique manner which is usually the site of

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 266 chemistry

chemical reactivity in an organic molecule. class suffix. In such cases the full name of the
Compounds having the same functional parent alkane is written before the class suffix.
group undergo similar reactions. For example, For example CH2(OH)CH2(OH) is named as
CH 3OH, CH 3CH 2OH, and (CH 3) 2CHOH — ethane–1,2–diol. However, the ending – ne of
all having -OH functional group liberate the parent alkane is dropped in the case of
hydrogen on reaction with sodium metal. compounds having more than one double or
The presence of functional groups enables triple bond; for example, CH2=CH-CH=CH2 is
systematisation of organic compounds into named as buta–1,3–diene.
different classes. Examples of some functional
groups with their prefixes and suffixes along Problem 8.8
with some examples of organic compounds Write the IUPAC names of the compounds
possessing these are given in Table 8.4. i-iv from their given structures.
First of all, the functional group present
in the molecule is identified which determines
the choice of appropriate suffix. The longest
chain of carbon atoms containing the
functional group is numbered in such a way
that the functional group is attached at the Solution
carbon atom possessing lowest possible • The functional group present is an
number in the chain. By using the suffix as alcohol (OH). Hence the suffix is ‘-ol’.
given in Table 8.4, the name of the compound • The longest chain containing -OH
is arrived at. has eight carbon atoms. Hence the
In the case of polyfunctional compounds, corresponding saturated hydrocar-
one of the functional groups is chosen as the bon is octane.
principal functional group and the compound • The -OH is on carbon atom 3. In
is then named on that basis. The remaining addition, a methyl group is attached
functional groups, which are subordinate at 6th carbon.
functional groups, are named as substituents Hence, the systematic name of this
using the appropriate prefixes. The choice of compound is 6-Methyloctan-3-ol.
principal functional group is made on the basis
of order of preference. The order of decreasing
priority for some functional groups is:
-COOH, –SO3H, -COOR (R=alkyl group), COCl,
-CONH2, -CN,-HC=O, >C=O, -OH, -NH2, >
C=C<, -C≡C- . Solution
The –R, C6H5-, halogens (F, Cl, Br, I), –NO2, The functional group present is ketone
alkoxy (–OR) etc. are always prefix (>C=O), hence suffix ‘-one’. Presence
substituents. Thus, a compound containing of two keto groups is indicated by ‘di’,
both an alcohol and a keto group is named hence suffix becomes ‘dione’. The two
as hydroxyalkanone since the keto group is keto groups are at carbons 2 and 4.
preferred to the hydroxyl group. The longest chain contains 6 carbon
For example, HOCH2(CH2)3CH2COCH3 will atoms, hence, parent hydrocarbon is
be named as 7-hydroxyheptan-2-one and not hexane. Thus, the systematic name is
as 2-oxoheptan -7-ol. Similarly, BrCH2CH=CH2 Hexane-2,4-dione.
is named as 3-bromoprop-1-ene and not
1-bromoprop-2-ene.
If more than one functional group of the
same type are present, their number is
indicated by adding di, tri, etc. before the

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Table 8.4 Some Functional Groups and Classes of Organic Compounds

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Solution (iii) Six membered ring containing a

Here, two functional groups namely carbon-carbon double bond is implied
ketone and carboxylic acid are present. by cyclohexene, which is numbered as
The principal functional group is the shown in (I). The prefix 3-nitro means
carboxylic acid group; hence the parent that a nitro group is present on C-3.
chain will be suffixed with ‘oic’ acid. Thus, complete structural formula of the
Numbering of the chain starts from compound is (II). Double bond is suffixed
carbon of – COOH functional group. functional group whereas NO2 is prefixed
The keto group in the chain at carbon functional group therefore double bond
5 is indicated by ‘oxo’. The longest gets preference over –NO2 group:
chain including the principal functional
group has 6 carbon atoms; hence the
parent hydrocarbon is hexane. The
compound is, therefore, named as
5-Oxohexanoic acid.

(iv) ‘1-ol’ means that a -OH group is

Solution present at C-1. OH is suffixed functional
The two C=C functional groups are group and gets preference over C=C
present at carbon atoms 1 and 3, while bond. Thus the structure is as shown
the C≡C functional group is present at in (II):
carbon 5. These groups are indicated by
suffixes ‘diene’ and ‘yne’ respectively. The
longest chain containing the functional
groups has 6 carbon atoms; hence the
parent hydrocarbon is hexane. The name
of compound, therefore, is Hexa-1,3-
dien-5-yne.
(v) ‘heptanal’ indicates the compound
Problem 8.9
to be an aldehyde containing 7 carbon
Derive the structure of (i) 2-Chlorohexane, atoms in the parent chain. The
(ii) Pent-4-en-2-ol, (iii) 3- Nitrocyclohexene, ‘6-hydroxy’ indicates that -OH group is
(iv) Cyclohex-2-en-1-ol, (v) 6-Hydroxy- present at carbon 6. Thus, the structural
heptanal. formula of the compound is: CH3CH(OH)
Solution CH2CH2CH2CH2CHO. Carbon atom of –
CHO group is included while numbering
(i) ‘hexane’ indicates the presence of
the carbon chain.
6 carbon atoms in the chain. The
functional group chloro is present at
carbon 2. Hence, the structure of the 8.5.4 Nomenclature of Substituted
compound is CH3CH2CH2CH2CH(Cl)CH3. Benzene Compounds
(ii) ‘pent’ indicates that parent
For IUPAC nomenclature of substituted
hydrocarbon contains 5 carbon atoms
benzene compounds, the substituent is
in the chain. ‘en’ and ‘ol’ correspond to
the functional groups C=C and -OH at placed as prefix to the word benzene as shown
carbon atoms 4 and 2 respectively. Thus, in the following examples. However, common
the structure is names (written in bracket below) of many
substituted benzene compounds are also
CH2=CHCH2CH (OH)CH3. universally used.

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 organic chemistry – some basic principles and techniques 269

Substituent of the base compound is

assigned number1 and then the direction
of numbering is chosen such that the
next substituent gets the lowest number.
The substituents appear in the name in
Methylbenzene Methoxybenzene Aminobenzene alphabetical order. Some examples are given
(Toluene) (Anisole) (Aniline)
below.

Nitrobenzene Bromobenzene 1-Chloro-2,4-dinitrobenzene

(not 4-chloro,1,3-dinitrobenzene)
If benzene ring is disubstituted,
the position of substituents is defined
by numbering the carbon atoms of the
ring such that the substituents are
located at the lowest numbers possible.
For example, the compound(b) is named
as 1,3-dibromobenzene and not as
1,5-dibromobenzene.

2-Chloro-1-methyl-4-nitrobenzene
(not 4-methyl-5-chloro-nitrobenzene)

(a) (b) (c)

1,2-Dibromo- 1,3-Dibromo- 1,4-Dibromo-
benzene benzene benzene
In the trivial system of nomenclature
the terms ortho (o), meta (m) and para (p) 2-Chloro-4-methylanisole 4-Ethyl-2-methylaniline
are used as prefixes to indicate the relative
positions 1,2;1,3 and 1,4 respectively. Thus,
1,3-dibr omobenzene (b) is named as
m-dibromobenzene (meta is abbreviated as
m-) and the other isomers of dibromobenzene
1,2-(a) and 1,4-(c), are named as ortho (or
just o-) and para (or just p-)-dibromobenzene,
respectively.
For tri - or higher substituted benzene 3,4-Dimethylphenol
derivatives, these prefixes cannot be used
and the compounds are named by identifying When a benzene ring is attached to an
substituent positions on the ring by following alkane with a functional group, it is considered
the lowest locant rule. In some cases, common as substituent, instead of a parent. The name
name of benzene derivatives is taken as the for benzene as substituent is phenyl (C6H5-,
base compound. also abbreviated as Ph).

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different carbon skeletons, these are referred

Problem 8.10
to as chain isomers and the phenomenon is
Write the structural formula of: termed as chain isomerism. For example,
(a) o-Ethylanisole, (b) p-Nitroaniline, C5H12 represents three compounds:
(c) 2,3 - Dibromo -1 - phenylpentane,
(d) 4-Ethyl-1-fluoro-2-nitrobenzene. CH3

Solution
CH3CH2CH2CH2CH3 CH3−CHCH2CH3
Pentane Isopentane
(2-Methylbutane)
CH3

CH3 C CH3
(a)  (b) 
CH3
Neopentane
(2,2-Dimethylpropane)

(ii) Position isomerism: When two or

more compounds differ in the position of
(c) (d) substituent atom or functional group on
the carbon skeleton, they are called position
8.6 ISOMERISM isomers and this phenomenon is termed
as position isomerism. For example, the
The phenomenon of existence of two or more molecular formula C3H 8O represents two
compounds possessing the same molecular alcohols:
formula but different properties is known
as isomerism. Such compounds are called OH
as isomers. The following flow chart shows 
different types of isomerism. CH3CH2CH2OH CH3−CH-CH3
Propan-1-ol Propan-2-ol
8.6.1 Structural Isomerism
Compounds having the same molecular (iii) Functional group isomerism: Two or
formula but different structures (manners more compounds having the same molecular
in which atoms are linked) are classified as formula but different functional groups
structural isomers. Some typical examples are called functional isomers and this
of different types of structural isomerism are phenomenon is termed as functional group
given below: isomerism. For example, the molecular
(i) Chain isomerism: When two or more formula C3H6O represents an aldehyde and
compounds have similar molecular formula but a ketone:
Isomerism

Structural isomerism Stereoisomerism

Chain Position Functional Metamerism Geometrical Optical

isomerism isomerism group isomerism isomerism
isomerism

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 organic chemistry – some basic principles and techniques 271

in understanding the reactivity of organic

O H compounds and in planning strategy for their
  synthesis.
CH3−C-CH3 CH3−CH2—C= O
In the following sections, we shall learn
Propanone Propanal
some of the principles that explain how these
(iv) Metamerism: It arises due to different reactions take place.
alkyl chains on either side of the functional
8.7.1 Fission of a Covalent Bond
group in the molecule. For example, C4H10O
represents methoxypropane (CH3OC3H7) and A covalent bond can get cleaved either by : (i)
ethoxyethane (C2H5OC2H5). heterolytic cleavage, or by (ii) homolytic
cleavage.
8.6.2 Stereoisomerism
In heterolytic cleavage, the bond breaks
The compounds that have the same in such a fashion that the shared pair of
constitution and sequence of covalent bonds electrons remains with one of the fragments.
but differ in relative positions of their atoms After heterolysis, one atom has a sextet
or groups in space are called stereoisomers. electronic structure and a positive charge and
This special type of isomerism is called as the other, a valence octet with at least one lone
stereoisomerism and can be classified as pair and a negative charge. Thus, heterolytic
geometrical and optical isomerism. +
cleavage of bromomethane will give C H3 and
8.7 F U N D A M E N TA L C O N C E P T S I N Br– as shown below.
ORGANIC REACTION MECHANISM
In an organic reaction, the organic molecule
(also referred as a substrate) reacts with an A species having a carbon atom possessing
appropriate attacking reagent and leads to sextext of electrons and a positive charge is
the formation of one or more intermediate(s) called a carbocation (earlier called carbonium
and finally product(s) ion). The H3 ion is known as a methyl cation
or methyl carbonium ion. Carbocations are
The general reaction is depicted as follows :
classified as primary, secondary or tertiary
Attacking depending on whether one, two or three
Reagent [Intermediate] Product(s)
Organic carbons are directly attached to the positively
molecule charged carbon. Some+ other examples of
(Substrate) Byproducts carbocations are: CH3C H2 (ethyl cation, a
+
primary carbocation), (CH3)2C H (isopropyl+
Substrate is that reactant which supplies cation, a secondary carbocation), and (CH3)3C
carbon to the new bond and the other reactant (tert-butyl cation, a tertiary carbocation).
is called reagent. If both the reactants Carbocations are highly unstable and
supply carbon to the new bond then choice reactive species. Alkyl groups directly
is arbitrary and in that case the molecule on attached to the positively charged carbon
which attention is focused is called substrate. stabilise the carbocations due to inductive
In such a reaction a covalent bond and hyperconjugation effects, which you will
between two carbon atoms or a carbon and be studying in the sections 8.7.5 and 8.7.9.
some other atom is broken and a new bond is The+ observed+ order of carbocation
+
stability
+
formed. A sequential account of each step, is: C H3 < CH3CH2 < (CH3)2CH < (CH3)3C. These
describing details of electron movement, carbocations have trigonal planar shape
energetics during bond cleavage and bond with positively charged carbon+ being sp 2
formation, and the rates of transformation hybridised. Thus, the shape of C H3 may be
of reactants into products (kinetics) is considered as being derived from the overlap
referred to as reaction mechanism. The of three equivalent C(sp2) hybridised orbitals
knowledge of reaction mechanism helps with 1s orbital of each of the three hydrogen

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 272 chemistry

atoms. Each bond may be represented as curved arrow. Such cleavage results in
C(sp 2)–H(1s) sigma bond. The remaining the formation of neutral species (atom or
carbon orbital is perpendicular to the group) which contains an unpaired electron.
molecular plane and contains no electrons. These species are called free radicals. Like
[Fig. 8.3(a)]. carbocations and carbanions, free radicals are
also very reactive. A homolytic cleavage can be
shown as:

Alkyl
free radical
Alkyl radicals are classified as primary,
secondary, or tertiary. Alkyl radical stability
increases as we proceed from primary to
Fig. 8.3 (a) Shape of methyl carbocation tertiary:
The heterolytic cleavage can also give a
,
species in which carbon gets the shared Methyl Ethyl Isopropyl Tert-butyl
pair of electrons. For example, when group free free free free
Z attached to the carbon leaves without radical radical radical radical
Organic reactions, which proceed by
homolytic fission are called free radical or
electron pair, the methyl anion is homopolar or nonpolar reactions.
formed. Such a carbon species carrying a 8.7.2 Substrate and Reagent
negative charge on carbon atom is called Ions are generally not formed in the reactions
carbanion. Carbon in carbanion is generally of organic compounds. Molecules as such
sp3 hybridised and its structure is distorted participate in the reaction. It is convenient to
tetrahedron as shown in Fig. 8.3(b). name one reagent as substrate and other as
reagent. In general, a molecule whose carbon
is involved in new bond formation is called
substrate and the other one is called reagent.
When carbon-carbon bond is formed, the
choice of naming the reactants as substrate
and reagent is arbitrary and depends on
molecule under observation. Example:

(i) CH2 = CH2 + Br2 →

Fig. 8.3 (b) Shape of methyl carbanion
CH2 Br – CH2Br
Substrate Reagent Product
Carbanions are also unstable and reactive
species. The organic reactions which proceed
through heterolytic bond cleavage are called (ii)
ionic or heteropolar or just polar reactions.
In homolytic cleavage, one of the electrons
of the shared pair in a covalent bond goes
with each of the bonded atoms. Thus, in
homolytic cleavage, the movement of a
single electron takes place instead of an Nucleophiles and Electrophiles
electron pair. The single electron movement Reagents attack the reactive site of the
is shown by ‘half-headed’ (fish hook: ) substrate. The reactive site may be electron

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 organic chemistry – some basic principles and techniques 273

deficient portion of the molecule (a positive

reactive site) e.g., an atom with incomplete Problem 8.11
electron shell or the positive end of the dipole Using curved-arrow notation, show the
in the molecule. If the attacking species is formation of reactive intermediates when
electron rich, it attacks these sites. If attacking the following covalent bonds undergo
species is electron deficient, the reactive site heterolytic cleavage.
for it is that part of the substrate molecule (a) CH3–SCH3, (b) CH3–CN, (c) CH3–Cu
which can supply electrons, e.g., π electrons Solution
in a double bond.
A reagent that brings an electron pair to
the reactive site is called a nucleophile (Nu:)
i.e., nucleus seeking and the reaction is then
called nucleophilic. A reagent that takes away
an electron pair from reactive site is called
electrophile (E+) i.e., electron seeking and the
reaction is called electrophilic. Problem 8.12
During a polar organic reaction, a Giving justification, categorise the
nucleophile attacks an electrophilic centre following molecules/ions as nucleophile
of the substrate which is that specific atom or electrophile:
or part of the substrate which is electron
deficient. Similarly, the electrophiles attack
at nucleophilic centre, which is the electron
rich centre of the substrate. Thus, the
electrophiles receive electron pair from the Solution
substrate when the two undergo bonding Nucleophiles: HS–,C2H5O–,(CH3)3N:H2N:–
interaction. A curved-arrow notation is used These species have unshared pair of
to show the movement of an electron pair electrons, which can be donated and
from the nucleophile to the electrophile. Some shared with an electrophile.
examples of nucleophiles are the negatively + + +
Electrophiles: BF 3 ,C1 H 3 –C =O,N O 2 .
charged ions with lone pair of electrons such Reactive sites have only six valence
as hydroxide (HO– ), cyanide (NC–) ions and electrons; can accept electron pair from
carbanions (R3C:–). Neutral molecules such a nucleophile.
as etc., can also act as
nucleophiles due to the presence of lone Problem 8.13
pair of electrons. Examples of electrophiles Identify electrophilic centre in the
+
include carbocations (C H 3 ) and neutral following: CH3CH=O, CH3CN, CH3I.
molecules having functional groups like Solution
carbonyl group (>C=O) or alkyl halides * *
A m o n g C H 3 H C = O , H 3 C C ≡N , a n d
(R 3C-X, where X is a halogen atom). The *
H3C –I, the starred carbon atoms are
carbon atom in carbocations has sextet
electrophilic centers as they will have
configuration; hence, it is electron deficient
and can receive a pair of electrons from the partial positive charge due to polarity of
nucleophiles. In neutral molecules such as the bond.
alkyl halides, due to the polarity of the C-X
bond a partial positive charge is generated 8.7.3 Electron Movement in Organic
on the carbon atom and hence the carbon Reactions
atom becomes an electrophilic centre at which The movement of electrons in organic
a nucleophile can attack. reactions can be shown by curved-arrow

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 274 chemistry

notation. It shows how changes in bonding 8.7.5 Inductive Effect

occur due to electronic redistribution during
When a covalent bond is formed between
the reaction. To show the change in position
atoms of different electronegativity, the
of a pair of electrons, curved arrow starts
electron density is more towards the more
from the point from where an electron pair is
electronegative atom of the bond. Such a shift
shifted and it ends at a location to which the
of electron density results in a polar covalent
pair of electron may move.
bond. Bond polarity leads to various electronic
Presentation of shifting of electron pair is effects in organic compounds.
given below : Let us consider cholorethane (CH3CH2Cl)
(i) from π bond to in which the C–Cl bond is a polar covalent
adjacent bond position bond. It is polarised in such a way that the
carbon-1 gains some positive charge (δ +)
(ii) from π bond to and the chlorine some negative charge (δ–).
adjacent atom The fractional electronic charges on the two
(iii) from atom to adjacent atoms in a polar covalent bond are denoted
bond position by symbol δ (delta) and the shift of electron
Movement of single electron is indicated by density is shown by an arrow that points from
a single barbed ‘fish hooks’ (i.e. half headed δ+ to δ– end of the polar bond.
curved arrow). For example, in transfer of δδ+ δ+ δ−
hydroxide ion giving ethanol and in the CH3→CH2→Cl
dissociation of chloromethane, the movement 2 1
of electron using curved arrows can be In turn carbon-1, which has developed
depicted as follows: partial positive charge (δ + ) draws some
electron density towards it from the adjacent
C-C bond. Consequently, some positive charge
(δδ+ ) develops on carbon-2 also, where δδ+
symbolises relatively smaller positive charge
as compared to that on carbon – 1. In other
words, the polar C – Cl bond induces polarity
8.7.4 Electron Displacement Effects in in the adjacent bonds. Such polarisation of
Covalent Bonds σ-bond caused by the polarisation of adjacent
σ-bond is referred to as the inductive effect.
The electron displacement in an organic This effect is passed on to the subsequent
molecule may take place either in the ground bonds also but the effect decreases rapidly
state under the influence of an atom or a as the number of intervening bonds increases
substituent group or in the presence of an and becomes vanishingly small after three
appropriate attacking reagent. The electron bonds. The inductive effect is related to the
displacements due to the influence of ability of substituent(s) to either withdraw or
an atom or a substituent group present in donate electron density to the attached carbon
the molecule cause permanent polarlisation atom. Based on this ability, the substitutents
of the bond. Inductive effect and resonance can be classified as electron-withdrawing or
effects are examples of this type of electron electron donating groups relative to hydrogen.
displacements. Temporary electron Halogens and many other groups such as
displacement effects are seen in a molecule nitro (- NO2), cyano (- CN), carboxy (- COOH),
when a reagent approaches to attack it. ester (COOR), aryloxy (-OAr, e.g. – OC6H5), etc.
This type of electron displacement is called are electron-withdrawing groups. On the other
electromeric effect or polarisability effect. hand, the alkyl groups like methyl (–CH3) and
In the following sections we will learn about ethyl (–CH2–CH3) are usually considered as
these types of electronic displacements. electron donating groups.
­

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benzene cannot be adequately represented

Problem 8.14 by any of these structures, rather it is
Which bond is more polar in the following a hybrid of the two structures (I and II)
pairs of molecules: (a) H3C-H, H3C-Br called resonance structures. The resonance
(b) H 3 C-NH 2 , H 3 C-OH (c) H 3 C-OH, structures (canonical structures or
H3C-SH contributing structures) are hypothetical
and individually do not represent any
Solution
real molecule. They contribute to the actual
(a) C–Br, since Br is more electronegative structure in proportion to their stability.
than H, (b) C–O, (c) C–O Another example of resonance is provided
Problem 8.15 by nitromethane (CH 3NO 2) which can be
In which C–C bond of CH3CH2CH2Br, the represented by two Lewis structures, (I and
inductive effect is expected to be the least? II). There are two types of N-O bonds in these
structures.
Solution
Magnitude of inductive effect diminishes
as the number of intervening bonds
increases. Hence, the effect is least in the
bond between carbon-3 and hydrogen.
However, it is known that the two N–O
8.7.6 Resonance Structure bonds of nitromethane are of the same
length (intermediate between a N–O single
There are many organic molecules whose bond and a N=O double bond). The actual
behaviour cannot be explained by a single Lewis structure of nitromethane is therefore
structure. An example is that of a resonance hybrid of the two canonical
benzene. Its cyclic structure forms I and II.
containing alternating C–C single The energy of actual structure of the molecule
and C=C double bonds shown (the resonance hybrid) is lower than that of
is inadequate for explaining its Benzene any of the canonical structures. The difference
characteristic properties. in energy between the actual structure and the
As per the above representation, benzene lowest energy resonance structure is called the
should exhibit two different bond lengths, resonance stabilisation energy or simply
due to C–C single and C=C double bonds. the resonance energy. The more the number
However, as determined experimentally of important contributing structures, the
benzene has a uniform C–C bond distances more is the resonance energy. Resonance is
particularly important when the contributing
of 139 pm, a value intermediate between the
structures are equivalent in energy.
C–C single(154 pm) and C=C double (134
pm) bonds. Thus, the structure of benzene The following rules are applied while writing
cannot be represented adequately by the resonance structures:
The resonance structures have (i) the same
above structure. Further, benzene can be
positions of nuclei and (ii) the same number of
represented equally well by the energetically
unpaired electrons. Among the resonance
identical structures I and II. structures, the one which has more number
of covalent bonds, all the atoms with octet
of electrons (except hydrogen which has a
duplet), less separation of opposite charges, (a
negative charge if any on more electronegative
atom, a positive charge if any on more
Therefore, according to the resonance electropositive atom) and more dispersal of
theory (Unit 4) the actual structure of charge, is more stable than others.

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Problem 8.16 Solution

Write resonance structures of CH3COO– The two structures are less important
and show the movement of electrons by contributors as they involve charge
curved arrows. separation. Additionally, structure
I contains a carbon atom with an
Solution
incomplete octet.
First, write the structure and put
unshared pairs of valence electrons on 8.7.7 Resonance Effect
appropriate atoms. Then draw the arrows
The resonance effect is defined as ‘the polarity
one at a time moving the electrons to get
produced in the molecule by the interaction
the other structures.
of two π-bonds or between a π-bond and
lone pair of electrons present on an adjacent
atom’. The effect is transmitted through the
chain. There are two types of resonance or
mesomeric effect designated as R or M effect.
Problem 8.17 (i) Positive Resonance Effect (+R effect)
Write resonance structures of In this effect, the transfer of electrons is away
CH2=CH–CHO. Indicate relative stability from an atom or substituent group attached
of the contributing structures. to the conjugated system. This electron
displacement makes certain positions in the
Solution
molecule of high electron densities. This effect
in aniline is shown as :

Stability: I > II > III (ii) Negative Resonance Effect (- R effect)

[I: Most stable, more number of covalent This effect is observed when the transfer of
bonds, each carbon and oxygen atom has electrons is towards the atom or substituent
an octet and no separation of opposite group attached to the conjugated system.
charge II: negative charge on more For example in nitrobenzene this electron
electronegative atom and positive charge displacement can be depicted as :
on more electropositive atom; III: does
not contribute as oxygen has positive
charge and carbon has negative charge,
hence least stable].
Problem 8.18
Explain why the following two structures,
I and II cannot be the major contributors The atoms or substituent groups, which
to the real structure of CH3COOCH3. represent +R or –R electron displacement
effects are as follows :
+R effect: – halogen, –OH, –OR, –OCOR, –NH2,
–NHR, –NR2, –NHCOR,
– R effect: – COOH, –CHO, >C=O, – CN, –NO2

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 organic chemistry – some basic principles and techniques 277

The presence of alternate single and system or to an atom with an unshared

double bonds in an open chain or cyclic system p orbital. The σ electrons of C—H bond of the
is termed as a conjugated system. These alkyl group enter into partial conjugation with
systems often show abnormal behaviour. the attached unsaturated system or with the
The examples are 1,3- butadiene, aniline unshared p orbital. Hyperconjugation is a
and nitrobenzene etc. In such systems, the permanent effect.
π-electrons are delocalised and the system To understand hyperconjugation effect, let
develops polarity. +
us take an example of CH3 C H2 (ethyl cation) in
8.7.8 Electromeric Effect (E effect) which the positively charged carbon atom has
It is a temporary effect. The organic compounds an empty p orbital. One of the C-H bonds of
having a multiple bond (a double or triple the methyl group can align in the plane of this
bond) show this effect in the presence of empty p orbital and the electrons constituting
an attacking reagent only. It is defined as the C-H bond in plane with this p orbital can
the complete transfer of a shared pair of then be delocalised into the empty p orbital
π-electrons to one of the atoms joined by a as depicted in Fig. 8.4 (a).
multiple bond on the demand of an attacking
reagent. The effect is annulled as soon as the
attacking reagent is removed from the domain
of the reaction. It is represented by E and the
shifting of the electrons is shown by a curved
arrow ( ). There are two distinct types of
electromeric effect.
(i) Positive Eelctromeric Effect (+E effect) In
this effect the π−electrons of the multiple
bond are transferred to that atom to which
the reagent gets attached. For example:
Fig. 8.4(a) Orbital diagram showing
hyperconjugation in ethyl cation

This type of overlap stabilises the

carbocation because electron density from
(ii) Negative Electromeric Effect (–E effect) In the adjacent σ bond helps in dispersing the
this effect the π - electrons of the multiple positive charge.
bond are transferred to that atom to which
the attacking reagent does not get attached.
For example:

When inductive and electromeric effects

operate in opposite directions, the electomeric
effect predominates.
In general, greater the number of alkyl
8.7.9 Hyperconjugation groups attached to a positively charged carbon
Hyperconjugation is a general stabilising atom, the greater is the hyperconjugation
interaction. It involves delocalisation of interaction and stabilisation of the cation.
σ electrons of C—H bond of an alkyl group Thus, we have the following relative stability
directly attached to an atom of unsaturated of carbocations :

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Problem 8.19 +
Explain why (CH 3) 3C is more stable
+ +
than CH3C H2 and C H3 is the least stable
cation.
Hyperconjugation is also possible in Solution
alkenes and alkylarenes. +
Hyperconjugation interaction in (CH3)3C is+
Delocalisation of electrons by +
greater than in CH3C H2 as the (CH3)3C
hyperconjugation in the case of alkene can +
has nine C-H bonds. In C H3, vacant p
be depicted as in Fig. 8.4(b).
orbital is perpendicular to the plane
in which C-H bonds lie; hence cannot
+
overlap with it. Thus, C H 3 lacks
hyperconjugative stability.

8.7.10 Types of Organic Reactions and

Mechanisms
Organic reactions can be classified into the
Fig. 8.4(b) Orbital diagram showing following categories:
hyperconjugation in propene (i) Substitution reactions
(ii) Addition reactions
There are various ways of looking at the (iii) Elimination reactions
hyperconjugative effect. One of the way is to (iv) Rearrangement reactions
regard C—H bond as possessing partial ionic
character due to resonance. You will be studying these reactions in
Unit 9 and later in class XII.
8.8 Methods of Purification of
Organic Compounds
Once an organic compound is extracted
from a natural source or synthesised in the
laboratory, it is essential to purify it. Various
methods used for the purification of organic
compounds are based on the nature of the
compound and the impurity present in it.
The common techniques used for
purification are as follows :
(i) Sublimation
(ii) Crystallisation
(iii) Distillation
(iv) Differential extraction and
(v) Chromatography
Finally, the purity of a compound is
ascertained by determining its melting or
boiling point. Most of the pure compounds
have sharp melting points and boiling points.
The hyperconjugation may also be New methods of checking the purity of an
regarded as no bond resonance. organic compound are based on different

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 organic chemistry – some basic principles and techniques 279

types of chromatographic and spectroscopic carefully. On boiling, the vapours of lower

techniques. boiling component are formed first. The
vapours are condensed by using a condenser
8.8.1 Sublimation
and the liquid is collected in a receiver.
You have learnt earlier that on heating, some The vapours of higher boiling component
solid substances change from solid to vapour form later and the liquid can be collected
state without passing through liquid state. separately.
The purification technique based on the above
principle is known as sublimation and is used
to separate sublimable compounds from non-
sublimable impurities.
8.8.2 Crystallisation
This is one of the most commonly used
techniques for the purification of solid organic
compounds. It is based on the difference in
the solubilities of the compound and the
impurities in a suitable solvent. The impure
compound is dissolved in a solvent in which it
is sparingly soluble at room temperature but
appreciably soluble at higher temperature.
The solution is concentrated to get a nearly
saturated solution. On cooling the solution,
pure compound crystallises out and is
removed by filtration. The filtrate (mother
liquor) contains impurities and small quantity
of the compound. If the compound is highly
soluble in one solvent and very little soluble
in another solvent, crystallisation can be Fig.8.5 Simple distillation. The vapours of a
satisfactorily carried out in a mixture of these substance formed are condensed and
the liquid is collected in conical flask.
solvents. Impurities, which impart colour to
the solution are removed by adsorbing over
activated charcoal. Repeated crystallisation Fractional Distillation: If the difference
becomes necessary for the purification in boiling points of two liquids is not much,
of compounds containing impurities of simple distillation cannot be used to separate
comparable solubilities. them. The vapours of such liquids are formed
within the same temperature range and are
8.8.3 Distillation condensed simultaneously. The technique of
This important method is used to separate fractional distillation is used in such cases. In
(i) volatile liquids from nonvolatile impurities this technique, vapours of a liquid mixture are
and (ii) the liquids having sufficient difference passed through a fractionating column before
in their boiling points. Liquids having condensation. The fractionating column is
different boiling points vaporise at different fitted over the mouth of the round bottom
temperatures. The vapours are cooled and flask (Fig.8.6, page 280).
the liquids so formed are collected separately. Vapours of the liquid with higher boiling
Chloroform (b.p 334 K) and aniline (b.p. 457 point condense before the vapours of the
K) are easily separated by the technique of liquid with lower boiling point. The vapours
distillation (Fig 8.5). The liquid mixture is rising up in the fractionating column become
taken in a round bottom flask and heated richer in more volatile component. By the

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 280 chemistry

unit in the fractionating column is called a

theoretical plate. Commercially, columns
with hundreds of plates are available.
One of the technological applications of
fractional distillation is to separate different
fractions of crude oil in petroleum industry.
Distillation under reduced
pressure: This method is
used to purify liquids having
very high boiling points and
those, which decompose at
or below their boiling points.
Such liquids are made to boil
at a temperature lower than
their normal boiling points
by reducing the pressure on
their surface. A liquid boils
at a temperature at which its
vapour pressure is equal to
the external pressure. The
pressure is reduced with
the help of a water pump
or vacuum pump (Fig.8.8).
Glycerol can be separated from
Fig.8.6 Fractional distillation. The vapours of lower boiling spent-lye in soap industry by
fraction reach the top of the column first followed by using this technique.
vapours of higher boiling fractions.

time the vapours reach to the top of the

fractionating column, these are rich in the
more volatile component. Fractionating
columns are available in various sizes and
designs as shown in Fig.8.7. A fractionating
column provides many surfaces for heat
exchange between the ascending vapours
and the descending condensed liquid. Some
of the condensing liquid in the fractionating
column obtains heat from the ascending
vapours and revaporises. The vapours thus
become richer in low boiling component. The
vapours of low boiling component ascend
to the top of the column. On reaching the
top, the vapours become pure in low boiling
component and pass through the condenser
and the pure liquid is collected in a receiver.
After a series of successive distillations, the
remaining liquid in the distillation flask gets
enriched in high boiling component. Each
Fig.8.7 Different types of fractionating columns.
successive condensation and vaporisation

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 organic chemistry – some basic principles and techniques 281

Fig.8.8 Distillation under reduced pressure. A liquid boils at a temperature below its
vapour pressure by reducing the pressure.

Steam Distillation: This technique is 8.8.4 Differential Extraction

applied to separate substances which are When an organic compound is present in an
steam volatile and are immiscible with water. aqueous medium, it is separated by shaking
In steam distillation, steam from a steam it with an organic solvent in which it is more
generator is passed through a heated flask soluble than in water. The organic solvent and
containing the liquid to be distilled. The the aqueous solution should be immiscible
mixture of steam and the volatile organic with each other so that they form two distinct
compound is condensed and collected. The layers which can be separated by separatory
compound is later separated from water using funnel. The organic solvent is later removed
a separating funnel. In steam distillation, by distillation or by evaporation to get back
the liquid boils when the sum of vapour the compound. Differential extraction is
pressures due to the organic liquid (p1) carried out in a separatory funnel as shown in
and that due to water (p2) becomes equal to Fig. 8.10 (Page 282). If the organic compound
the atmospheric pressure (p), i.e. p =p1+ p2. is less soluble in the organic solvent, a very
Since p1 is lower than p, the organic liquid large quantity of solvent would be required
vaporises at lower temperature than its to extract even a very small quantity of the
boiling point. compound. The technique of continuous
Thus, if one of the substances in the extraction is employed in such cases. In this
mixture is water and the other, a water technique same solvent is repeatedly used for
insoluble substance, then the mixture will boil extraction of the compound.
close to but below, 373K. A mixture of water 8.8.5 Chromatography
and the substance is obtained which can Chromatography is an important technique
be separated by using a separating funnel. extensively used to separate mixtures into
Aniline is separated by this technique from their components, purify compounds and
aniline – water mixture (Fig.8.9, Page 282). also to test the purity of compounds. The

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 282 chemistry

Fig.8.9 Steam distillation. Steam volatile component volatilizes, the vapours condense
in the condenser and the liquid collects in conical flask.
name chromatography is based on the Greek
word chroma, for colour since the method
was first used for the separation of coloured
substances found in plants. In this technique,
the mixture of substances is applied onto a
stationary phase, which may be a solid or a
liquid. A pure solvent, a mixture of solvents,
or a gas is allowed to move slowly over the
stationary phase. The components of the
mixture get gradually separated from one
another. The moving phase is called the
mobile phase.
Based on the principle involved,
chromatography is classified into different
categories. Two of these are:
(a) Adsorption chromatography, and Fig.8.10 Differential extraction. Extraction of com-
(b) Partition chromatography. pound takes place based on difference
in solubility
a) Adsorption Chromatography: Adsor-
ption chromatography is based on the fact
that different compounds are adsorbed on distances over the stationary phase. Following
an adsorbent to different degrees. Commonly are two main types of chromatographic
used adsorbents are silica gel and alumina. techniques based on the principle of differential
When a mobile phase is allowed to move adsorption.
over a stationary phase (adsorbent), the (a) Column chromatography, and
components of the mixture move by varying (b) Thin layer chromatography.

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 organic chemistry – some basic principles and techniques 283

Column Chromatography: Column The glass plate is then placed in a closed jar
chromatography involves separation of containing the eluant (Fig. 8.12a). As the
a mixture over a column of adsorbent eluant rises up the plate, the components of
(stationary phase) packed in a glass tube. the mixture move up along with the eluant to
The column is fitted with a stopcock at its different distances depending on their degree
lower end (Fig. 8.11). The mixture adsorbed of adsorption and separation takes place.
on adsorbent is placed on the top of the The relative adsorption of each component
adsorbent column packed in a glass tube. of the mixture is expressed in terms of its
An appropriate eluant which is a liquid or a retardation factor i.e. Rf value (Fig.8.12 b).
mixture of liquids is allowed to flow down the Rf = Distance moved by the substance from base line (x)
column slowly. Depending upon the degree to Distance moved by the solvent from base line (y)
which the compounds are adsorbed, complete
separation takes place. The most readily
adsorbed substances are retained near the top
and others come down to various distances
in the column (Fig.8.11).

Fig.8.12 (a) T h i n l a y e r c h ro m a t o g r a p h y .
Chromatogram being developed.

Fig.8.11 Column chromatography. Different

stages of separation of components Fig.8.12 (b) Developed chromatogram.
of a mixture.
The spots of coloured compounds are
Thin Layer Chromatography: Thin layer visible on TLC plate due to their original colour.
chromatography (TLC) is another type of The spots of colourless compounds, which are
adsorption chromatography, which involves invisible to the eye but fluoresce in ultraviolet
separation of substances of a mixture over light, can be detected by putting the plate under
a thin layer of an adsorbent coated on glass ultraviolet light. Another detection technique
plate. A thin layer (about 0.2mm thick) of is to place the plate in a covered jar containing
an adsorbent (silica gel or alumina) is spread a few crystals of iodine. Spots of compounds,
over a glass plate of suitable size. The plate which adsorb iodine, will show up as brown
is known as thin layer chromatography plate spots. Sometimes an appropriate reagent
or chromaplate. The solution of the mixture may also be sprayed on the plate. For example,
to be separated is applied as a small spot amino acids may be detected by spraying the
about 2 cm above one end of the TLC plate. plate with ninhydrin solution (Fig.8.12b).

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Partition Chromatography: Partition spot on the chromatogram. The spots of the

chromatography is based on continuous separated colourless compounds may be
differential partitioning of components of observed either under ultraviolet light or by
a mixture between stationary and mobile the use of an appropriate spray reagent as
phases. Paper chromatography is a type discussed under thin layer chromatography.
of partition chromatography. In paper
8.9 Qualitative Analysis of Organic
chromatography, a special quality paper
Compounds
known as chromatography paper is used.
Chromatography paper contains water trapped The elements present in organic compounds
in it, which acts as the stationary phase. are carbon and hydrogen. In addition to
A strip of chromatography paper spotted these, they may also contain oxygen, nitrogen,
at the base with the solution of the mixture is sulphur, halogens and phosphorus.
suspended in a suitable solvent or a mixture 8.9.1 Detection of Carbon and Hydrogen
of solvents (Fig. 8.13). This solvent acts as the Carbon and hydrogen are detected by heating
mobile phase. The solvent rises up the paper the compound with copper(II) oxide. Carbon
by capillary action and flows over the spot. The present in the compound is oxidised to
paper selectively retains different components carbon dioxide (tested with lime-water, which
according to their differing partition in the develops turbidity) and hydrogen to water
two phases. The paper strip so developed is (tested with anhydrous copper sulphate,
known as a chromatogram. The spots of the which turns blue).
separated coloured compounds are visible at C + 2CuO 2Cu + CO2
different heights from the position of initial 2H + CuO Cu + H2O
CO2 + Ca(OH)2 CaCO3↓ + H2O
5H2O + CuSO4 CuSO4.5H2O
White Blue
8.9.2 Detection of Other Elements
Nitrogen, sulphur, halogens and phosphorus
present in an organic compound are detected
by “Lassaigne’s test”. The elements present
in the compound are converted from covalent
form into the ionic form by fusing the
compound with sodium metal. Following
reactions take place:
Na + C + N NaCN
2Na + S Na2S
Na + X Na X
(X = Cl, Br or I)
C, N, S and X come from organic compound.
Cyanide, sulphide and halide of sodium so
formed on sodium fusion are extracted from
the fused mass by boiling it with distilled
water. This extract is known as sodium fusion
extract.
(A) Test for Nitrogen
Fig.8.13 Paper chromatography.
Chromatography paper in two different The sodium fusion extract is boiled with
shapes. iron(II) sulphate and then acidified with

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 organic chemistry – some basic principles and techniques 285

concentrated sulphuric acid. The formation bromine and a yellow precipitate, insoluble
of Prussian blue colour confirms the presence in ammonium hydroxide shows the presence
of nitrogen. Sodium cyanide first reacts of iodine.
with iron(II) sulphate and forms sodium X– + Ag+ → AgX
hexacyanidoferrate(II). On heating with X represents a halogen – Cl, Br or I.
concentrated sulphuric acid some iron(II)
If nitrogen or sulphur is also present in the
ions are oxidised to iron(III) ions which
compound, the sodium fusion extract is
react with sodium hexacyanidoferrate(II)
first boiled with concentrated nitric acid to
to produce iron(III) hexacyanidoferrate(II) decompose cyanide or sulphide of sodium
(ferriferrocyanide) which is Prussian blue in formed during Lassaigne’s test. These ions
colour. would otherwise interfere with silver nitrate
6CN– + Fe2+ → [Fe(CN)6]4– test for halogens.
3[Fe(CN)6]4– + 4Fe3+ Fe4[Fe(CN)6]3.xH2O (D) Test for Phosphorus
 Prussian blue The compound is heated with an oxidising
(B) Test for Sulphur agent (sodium peroxide). The phosphorus
(a) The sodium fusion extract is acidified present in the compound is oxidised to
with acetic acid and lead acetate is added phosphate. The solution is boiled with nitric
to it. A black precipitate of lead sulphide acid and then treated with ammonium
indicates the presence of sulphur. molybdate. A yellow colouration or precipitate
indicates the presence of phosphorus.
S2– + Pb2+ → PbS
Black Na3PO4 + 3HNO3 → H3PO4+3NaNO3
(b) On treating sodium fusion extract with H3PO4 + 12(NH4)2MoO4 + 21HNO3 →
sodium nitroprusside, appearance of Ammonium
a violet colour further indicates the molybdate
presence of sulphur. (NH4)3PO4.12MoO3 + 21NH4NO3 + 12H2O
S2– + [Fe(CN)5NO]2– → [Fe(CN)5NOS]4– Ammonium
Violet phosphomolybdate
In case, nitrogen and sulphur both are 8.10 Quantitative Analysis
present in an organic compound, sodium
Quantitative analysis of compounds is very
thiocyanate is formed. It gives blood red colour
important in organic chemistry. It helps
and no Prussian blue since there are no free
chemists in the determination of mass per
cyanide ions.
cent of elements present in a compound. You
Na + C + N + S → NaSCN
have learnt in Unit-1 that mass per cent of
Fe +SCN
3+ –
→ [Fe(SCN)]2+ elements is required for the determination of

Blood red emperical and molecular formula.
If sodium fusion is carried out with excess The percentage composition of elements
of sodium, the thiocyanate decomposes to present in an organic compound is determined
yield cyanide and sulphide. These ions give by the following methods:
their usual tests.
NaSCN + 2Na → NaCN+Na2S 8.10.1 Carbon and Hydrogen
(C) Test for Halogens Both carbon and hydrogen are estimated in
one experiment. A known mass of an organic
The sodium fusion extract is acidified with
compound is burnt in the presence of excess
nitric acid and then treated with silver nitrate.
of oxygen and copper(II) oxide. Carbon and
A white precipitate, soluble in ammonium
hydrogen in the compound are oxidised to
hydroxide shows the presence of chlorine,
carbon dioxide and water respectively.
a yellowish precipitate, sparingly soluble in
ammonium hydroxide shows the presence of CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O

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Fig.8.14 Estimation of carbon and hydrogen. Water and carbon dioxide formed on oxidation of substance
are absorbed in anhydrous calcium chloride and potassium hydroxide solutions respectively
contained in U tubes.

The mass of water produced is determined 8.10.2 Nitrogen

by passing the mixture through a weighed There are two methods for estimation of
U-tube containing anhydrous calcium chloride. nitrogen: (i) Dumas method and (ii) Kjeldahl’s
Carbon dioxide is absorbed in another U-tube method.
containing concentrated solution of potassium (i) Dumas method: The nitrogen containing
hydroxide. These tubes are connected in series organic compound, when heated with copper
(Fig. 8.14). The increase in masses of calcium oxide in an atmosphere of carbon dioxide,
chloride and potassium hydroxide gives the yields free nitrogen in addition to carbon
amounts of water and carbon dioxide from dioxide and water.
which the percentages of carbon and hydrogen
CxHyNz + (2x + y/2) CuO →
are calculated.
Let the mass of organic compound be x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
m g, mass of water and carbon dioxide
Traces of nitrogen oxides formed, if
produced be m1 and m2 g respectively;
any, are reduced to nitrogen by passing the
12 × m2 × 100 gaseous mixture over a heated copper gauze.
Percentage of carbon=
44 × m The mixture of gases so produced is collected
2 × m1 × 100 over an aqueous solution of potassium
Percentage of hydrogen = hydroxide which absorbs carbon dioxide.
18 × m Nitrogen is collected in the upper part of the
Problem 8.20 graduated tube (Fig.8.15).
On complete combustion, 0.246 g of an Let the mass of organic compound = m g
organic compound gave 0.198g of carbon Volume of nitrogen collected = V1 mL
dioxide and 0.1014g of water. Determine
Room temperature = T1K
the percentage composition of carbon
and hydrogen in the compound. 1 1 × 273
PV
Volume of nitrogen at STP =
Solution 760 × T1
12 × 0.198 × 100 (Let it be V mL)
Percentage of carbon =
44 × 0.246 Where p 1 and V 1 are the pressure and
= 21.95% volume of nitrogen, p1 is different from the
atmospheric pressure at which nitrogen gas
2 × 0.1014 × 100 is collected. The value of p1 is obtained by
Percentage of hydrogen =
18 × 0.246 the relation;
= 4.58% p1= Atmospheric pressure – Aqueous tension
22400 mL N2 at STP weighs 28 g.

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 organic chemistry – some basic principles and techniques 287

Fig. 8.15 Dumas method. The organic compound yields nitrogen gas on heating it with
copper(II) oxide in the presence of CO2 gas. The mixture of gases is collected over
potassium hydroxide solution in which CO2 is absorbed and volume of nitrogen
gas is determined.

28 × V
V mL N 2 at STP weighs = g 28 × 41.9
22400 41.9 mL of nitrogen weighs = g
22400
28 × V × 100
Percentage of nitrogen = 28 × 41.9 × 100
22400 × m Percentage of nitrogen =
22400 × 0.3
Problem 8.21 = 17.46%
In Dumas’ method for estimation of
nitrogen, 0.3g of an organic compound
gave 50mL of nitrogen collected at 300K
temperature and 715mm pressure. (ii) Kjeldahl’s method: The compound
Calculate the percentage composition containing nitrogen is heated with concentrated
of nitrogen in the compound. (Aqueous sulphuric acid. Nitrogen in the compound
tension at 300K=15 mm) gets converted to ammonium sulphate
(Fig. 8.16). The resulting acid mixture is then
Solution
heated with excess of sodium hydroxide.
Volume of nitrogen collected at 300K and The liberated ammonia gas is absorbed in
715mm pressure is 50 mL an excess of standard solution of sulphuric
Actual pressure = 715-15 =700 mm acid. The amount of ammonia produced is
273 × 700 × 50 determined by estimating the amount of
Volume of nitrogen at STP sulphuric acid consumed in the reaction. It
300 × 760
is done by estimating unreacted sulphuric
41.9 mL
acid left after the absorption of ammonia by
22,400 mL of N2 at STP weighs = 28 g titrating it with standard alkali solution. The
difference between the initial amount of acid

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Fig.8.16 Kjeldahl method. Nitrogen-containing compound is treated with concentrated H2SO4 to get
ammonium sulphate which liberates ammonia on treating with NaOH; ammonia is absorbed
in known volume of standard acid.
taken and that left after the reaction gives the 14 × M × 2(V − V1 / 2) 100
amount of acid reacted with ammonia. Percentage of N = ×
1000 m
Organic compound + H2SO4 → (NH4)2SO4
1.4 × M × 2 (V − V / 2)
Na2SO4 + 2NH3 + 2H2O =
m
2NH3 + H2SO4 → (NH4)2SO4
Kjeldahl method is not applicable to
Let the mass of organic compound taken = m g compounds containing nitrogen in nitro and
Volume of H2SO4 of molarity, M, azo groups and nitrogen present in the ring
taken = V mL (e.g. pyridine) as nitrogen of these compounds
Volume of NaOH of molarity, M, used for does not change to ammonium sulphate
titration of excess of H2SO4 = V1 mL under these conditions.
V1mL of NaOH of molarity M
Problem 8.22
= V1 /2 mL of H2SO4 of molarity M
Volume of H 2 SO 4 of molarity M unused During estimation of nitrogen present
= (V - V1/2) mL in an organic compound by Kjeldahl’s
method, the ammonia evolved from
(V- V1/2) mL of H2SO4 of molarity M 0.5 g of the compound in Kjeldahl’s
= 2(V-V1/2) mL of NH3 solution of estimation of nitrogen, neutralized 10 mL
molarity M. of 1 M H2SO4. Find out the percentage of
1000 mL of 1 M NH 3 solution contains nitrogen in the compound.
17g NH3 or 14 g of N Solution
2(V-V1/2) mL of NH3 solution of molarity M 1 M of 10 mL H2SO4=1M of 20 mL NH3
contains: 1000 mL of 1M ammonia contains 14 g
14 × M × 2(V − V1 / 2) nitrogen
gN
1000 20 mL of 1M ammonia contains

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 organic chemistry – some basic principles and techniques 289

14 × 20 Percentage of halogen
g nitrogen
1000 atomic mass of X × m1g
=
14×20×100 molecular mass of AgX
Percentage of nitrogen = = 56.0%
1000×0.5
Problem 8.23
8.10.3 Halogens In Carius method of estimation of
Carius method: A known mass of an organic halogen, 0.15 g of an organic compound
compound is heated with fuming nitric acid in gave 0.12 g of AgBr. Find out the
the presence of silver nitrate contained in a hard percentage of bromine in the compound.
glass tube known as Carius tube, (Fig.8.17) Solution
Molar mass of AgBr = 108 + 80
= 188 g mol-1
188 g AgBr contains 80 g bromine
80 × 0.12
0.12 g AgBr contains g bromine
188

80 × 0.12 × 100
Percentage of bromine =
188×0.15
= 34.04%

8.10.4 Sulphur
A known mass of an organic compound is
heated in a Carius tube with sodium peroxide
or fuming nitric acid. Sulphur present in the
compound is oxidised to sulphuric acid. It
is precipitated as barium sulphate by adding
excess of barium chloride solution in water.
The precipitate is filtered, washed, dried and
weighed. The percentage of sulphur can be
Fig. 8.17 Carius method. Halogen containing calculated from the mass of barium sulphate.
organic compound is heated with fuming
nitric acid in the presence of silver
Let the mass of organic
nitrate. compound taken = m g
and the mass of barium
in a furnace. Carbon and hydrogen present in sulphate formed = m1g
the compound are oxidised to carbon dioxide 1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur
and water. The halogen present forms the 32 × m1 × 100
corresponding silver halide (AgX). It is filtered, m1 g BaSO4 contains g sulphur
233 × m
washed, dried and weighed.
32 × m1 × 100
Let the mass of organic Percentage of sulphur =
compound taken = m g 233 × m
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of X
Mass of halogen in m1g of AgX Problem 8.24
atomic mass of X × m1g In sulphur estimation, 0.157 g of an
= organic compound gave 0.4813 g of
molecular mass of AgX

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percentage composition (100) and the sum of

barium sulphate. What is the percentage
the percentages of all other elements. However,
of sulphur in the compound?
oxygen can also be estimated directly as follows:
Solution A definite mass of an organic compound is
Molecular mass of BaSO4 = 137+32+64 decomposed by heating in a stream of nitrogen
gas. The mixture of gaseous products containing
= 233 g
oxygen is passed over red-hot coke when all
233 g BaSO4 contains 32 g sulphur the oxygen is converted to carbon monoxide.
32 × 0.4813 This mixture is passed through warm iodine
0.4813 g BaSO4 contains g pentoxide (I2O5) when carbon monoxide is
g sulphur 233
oxidised to carbon dioxide producing iodine.
32 × 0.4813 × 100 Compound  heat
→ O2 + other gaseous
Percentage of sulphur = products
233 × 0.157
2C + O2 
1373 K
→ 2CO]× 5 (A)
= 42.10%
I2O5 + 5CO → I2 + 5CO2]× 2 (B)

8.10.5 Phosphorus On making the amount of CO produced in

A known mass of an organic compound is equation (A) equal to the amount of CO used
heated with fuming nitric acid whereupon in equation (B) by multiplying the equations
phosphorus present in the compound is (A) and (B) by 5 and 2 respectively; we find
oxidised to phosphoric acid. It is precipitated that each mole of oxygen liberated from
as ammonium phosphomolybdate, (NH4)3 the compound will produce two moles of
PO 4 .12MoO 3 , by adding ammonia and carbondioxide.
ammonium molybdate. Alter natively, Thus 88 g carbon dioxide is obtained if 32 g
phosphoric acid may be precipitated as oxygen is liberated.
MgNH4PO4 by adding magnesia mixture which Let the mass of organic compound taken be m g
on ignition yields Mg2P2O7. Mass of carbon dioxide produced be m1 g
Let the mass of organic compound taken ∴ m 1 g carbon dioxide is obtained from
= m g and mass of ammonium phospho 32 × m1
molydate = m1g g O2
88
Molar mass of (NH4)3PO4.12MoO3 = 1877g 32 × m1 × 100
∴Percentage of oxygen = %
31 × m1 × 100 88 × m
Percentage of phosphorus = %
1877 × m The percentage of oxygen can be derived
from the amount of iodine produced also.
If phosphorus is estimated as Mg2P2O7,
Presently, the estimation of elements in
62 × m1 × 100 an organic compound is carried out by using
Percentage of phosphorus = ×%
222 microquantities of substances and automatic
where, 222 u is the molar mass of Mg2P2O7, experimental techniques. The elements,
m, the mass of organic compound taken, carbon, hydrogen and nitrogen present in a
m1, the mass of Mg2P2O7 formed and 62, the compound are determined by an apparatus
mass of two phosphorus atoms present in the known as CHN elemental analyser. The
compound Mg2P2O7. analyser requires only a very small amount
of the substance (1-3 mg) and displays the
8.10.6 Oxygen values on a screen within a short time. A
The percentage of oxygen in an organic compound detailed discussion of such methods is beyond
is usually found by difference between the total the scope of this book.

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Summary

In this unit, we have learnt some basic concepts in structure and reactivity of organic
compounds, which are formed due to covalent bonding. The nature of the covalent bonding
in organic compounds can be described in terms of orbitals hybridisation concept,
according to which carbon can have sp3, sp2 and sp hybridised orbitals. The sp3, sp2 and sp
hybridised carbons are found in compounds like methane, ethene and ethyne respectively.
The tetrahedral shape of methane, planar shape of ethene and linear shape of ethyne can
be understood on the basis of this concept. A sp3 hybrid orbital can overlap with 1s orbital
of hydrogen to give a carbon - hydrogen (C–H) single bond (sigma, σ bond). Overlap of a sp2
orbital of one carbon with sp2 orbital of another results in the formation of a carbon–carbon
σ bond. The unhybridised p orbitals on two adjacent carbons can undergo lateral (side-
by-side) overlap to give a pi (π) bond. Organic compounds can be represented by various
structural formulas. The three dimensional representation of organic compounds on paper
can be drawn by wedge and dash formula.
Organic compounds can be classified on the basis of their structure or the functional
groups they contain. A functional group is an atom or group of atoms bonded together in a
unique fashion and which determines the physical and chemical properties of the compounds.
The naming of the organic compounds is carried out by following a set of rules laid down by
the International Union of Pure and Applied Chemistry (IUPAC). In IUPAC nomenclature,
the names are correlated with the structure in such a way that the reader can deduce the
structure from the name.
Organic reaction mechanism concepts are based on the structure of the substrate
molecule, fission of a covalent bond, the attacking reagents, the electron displacement effects
and the conditions of the reaction. These organic reactions involve breaking and making
of covalent bonds. A covalent bond may be cleaved in heterolytic or homolytic fashion.
A heterolytic cleavage yields carbocations or carbanions, while a homolytic cleavage gives
free radicals as reactive intermediate. Reactions proceeding through heterolytic cleavage
involve the complimentary pairs of reactive species. These are electron pair donor known as
nucleophile and an electron pair acceptor known as electrophile. The inductive, resonance,
electromeric and hyperconjugation effects may help in the polarisation of a bond making
certain carbon atom or other atom positions as places of low or high electron densities.
Organic reactions can be broadly classified into following types; substitution, addition,
elimination and rearrangement reactions.
Purification, qualitative and quantitative analysis of organic compounds are carried out
for determining their structures. The methods of purification namely : sublimation, distillation
and differential extraction are based on the difference in one or more physical properties.
Chromatography is a useful technique of separation, identification and purification of
compounds. It is classified into two categories : adsorption and partition chromatography.
Adsorption chromatography is based on differential adsorption of various components of a
mixture on an adsorbent. Partition chromatography involves continuous partitioning of the
components of a mixture between stationary and mobile phases. After getting the compound
in a pure form, its qualitative analysis is carried out for detection of elements present in it.
Nitrogen, sulphur, halogens and phosphorus are detected by Lassaigne’s test. Carbon and
hydrogen are estimated by determining the amounts of carbon dioxide and water produced.
Nitrogen is estimated by Dumas or Kjeldahl’s method and halogens by Carius method.
Sulphur and phosphorus are estimated by oxidising them to sulphuric and phosphoric acids
respectively. The percentage of oxygen is usually determined by difference between the total
percentage (100) and the sum of percentages of all other elements present.

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 292 chemistry

Exercises

8.1 What are hybridisation states of each carbon atom in the following compounds ?
CH2=C=O, CH3CH=CH2, (CH3)2CO, CH2=CHCN, C6H6
8.2 Indicate the σ and π bonds in the following molecules :
C6H6, C6H12, CH2Cl2, CH2=C=CH2, CH3NO2, HCONHCH3
8.3 Write bond line formulas for : Isopropyl alcohol, 2,3-Dimethylbutanal, Heptan-4-one.
8.4 Give the IUPAC names of the following compounds :

(a) (b) (c)

(d) (e) (f) Cl2CHCH2OH

8.5 Which of the following represents the correct IUPAC name for the compounds
concerned ? (a) 2,2-Dimethylpentane or 2-Dimethylpentane (b)
2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane (c) 2-Chloro-4-methylpentane or
4-Chloro-2-methylpentane (d) But-3-yn-1-ol or But-4-ol-1-yne.
8.6 Draw formulas for the first five members of each homologous series beginning with
the following compounds. (a) H–COOH (b) CH3COCH3 (c) H–CH=CH2
8.7 Give condensed and bond line structural formulas and identify the functional group(s)
present, if any, for :
(a) 2,2,4-Trimethylpentane
(b) 2-Hydroxy-1,2,3-propanetricarboxylic acid
(c) Hexanedial
8.8 Identify the functional groups in the following compounds

(a) (b) (c)

8.9 Which of the two: O2NCH2CH2O– or CH3CH2O– is expected to be more stable and
why?
8.10 Explain why alkyl groups act as electron donors when attached to a π system.
8.11 Draw the resonance structures for the following compounds. Show the electron shift
using curved-arrow notation.
+
(a) C 6 H 5 OH (b) C 6 H 5 NO 2 (c) CH 3 CH=CHCHO (d) C 6 H 5 –CHO (e) C 6 H 5 –CH 2
+
(f) CH3CH=CH C H2
8.12 What are electrophiles and nucleophiles ? Explain with examples.
8.13 Identify the reagents shown in bold in the following equations as nucleophiles or
electrophiles:
–
(a) CH3COOH + HO → CH3COO–+H2O

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 organic chemistry – some basic principles and techniques 293

–
(b) CH3COCH3+ CN → (CH3)2C(CN)(OH)
+
(c) C6H6 + CH3CO → C6H5COCH3
8.14 Classify the following reactions in one of the reaction type studied in this unit.
– –
(a) CH3CH2Br + HS → CH3CH2SH + Br
(b) (CH3)2C = CH2 + HCI → (CH3)2CIC – CH3
– –
(c) CH3CH2Br + HO → CH2 = CH2 + H2O + Br
(d) (CH3)3C– CH2OH + HBr → (CH3)2CBrCH2CH2CH3 + H2O
8.15 What is the relationship between the members of following pairs of structures ?
Are they structural or geometrical isomers or resonance contributors ?

(a)

(b)

(c)

8.16 For the following bond cleavages, use curved-arrows to show the electron flow and
classify each as homolysis or heterolysis. Identify reactive intermediate produced
as free radical, carbocation and carbanion.

(a)

(b)

(c)

(d)

8.17 Explain the terms Inductive and Electromeric effects. Which electron displacement
effect explains the following correct orders of acidity of the carboxylic acids?
(a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
(b) CH3CH2COOH > (CH3)2CHCOOH > (CH3)[Link]
8.18 Give a brief description of the principles of the following techniques taking an
example in each case.
(a) Crystallisation (b) Distillation (c) Chromatography
8.19 Describe the method, which can be used to separate two compounds with different
solubilities in a solvent S.
8.20 What is the difference between distillation, distillation under reduced pressure and
steam distillation ?

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 294 chemistry

8.21 Discuss the chemistry of Lassaigne’s test.

8.22 Differentiate between the principle of estimation of nitrogen in an organic compound
by (i) Dumas method and (ii) Kjeldahl’s method.
8.23 Discuss the principle of estimation of halogens, sulphur and phosphorus present
in an organic compound.
8.24 Explain the principle of paper chromatography.
8.25 Why is nitric acid added to sodium extract before adding silver nitrate for testing
halogens?
8.26 Explain the reason for the fusion of an organic compound with metallic sodium for
testing nitrogen, sulphur and halogens.
8.27 Name a suitable technique of separation of the components from a mixture of
calcium sulphate and camphor.
8.28 Explain, why an organic liquid vaporises at a temperature below its boiling point
in its steam distillation ?
8.29 Will CCl4 give white precipitate of AgCl on heating it with silver nitrate? Give reason
for your answer.
8.30 Why is a solution of potassium hydroxide used to absorb carbon dioxide evolved
during the estimation of carbon present in an organic compound?
8.31 Why is it necessary to use acetic acid and not sulphuric acid for acidification of
sodium extract for testing sulphur by lead acetate test?
8.32 An organic compound contains 69% carbon and 4.8% hydrogen, the remainder
being oxygen. Calculate the masses of carbon dioxide and water produced when
0.20 g of this substance is subjected to complete combustion.
8.33 A sample of 0.50 g of an organic compound was treated according to Kjeldahl’s
method. The ammonia evolved was absorbed in 50 ml of 0.5 M H2SO4. The residual
acid required 60 mL of 0.5 M solution of NaOH for neutralisation. Find the percentage
composition of nitrogen in the compound.
8.34 0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius
estimation. Calculate the percentage of chlorine present in the compound.
8.35 In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur
compound afforded 0.668 g of barium sulphate. Find out the percentage of sulphur
in the given compound.
8.36 In the organic compound CH2 = CH – CH2 – CH2 – C ≡ CH, the pair of hydridised
orbitals involved in the formation of: C2 – C3 bond is:
(a) sp – sp2 (b) sp – sp3 (c) sp2 – sp3 (d) sp3 – sp3
8.37 In the Lassaigne’s test for nitrogen in an organic compound, the Prussian blue
colour is obtained due to the formation of:
(a) Na4[Fe(CN)6] (b) Fe4[Fe(CN)6]3 (c) Fe2[Fe(CN)6] (d) Fe3[Fe(CN)6]4
8.38 Which of the+ following carbocation+
is most+ stable ? +
(a) (CH3)3C. C­­­­­­­ H2 (b) (CH3)3C­­­  (c) CH3CH2C­­­  H2 (d) CH3C­­­  H CH2CH3
8.39 The best and latest technique for isolation, purification and separation of organic
compounds is:
(a) Crystallisation (b) Distillation (c) Sublimation (d) Chromatography
8.40 The reaction:
CH3CH2I + KOH(aq) → CH3CH2OH + KI
is classified as :
(a) electrophilic substitution (b) nucleophilic substitution
(c) elimination (d) addition

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 Hydrocarbons 295

Unit 9

Hydrocarbons

Hydrocarbons are the important sources of energy.

After studying this unit, you will be

able to
• name hydrocarbons according to The term ‘hydrocarbon’ is self-explanatory which means
IUPAC system of nomenclature; compounds of carbon and hydrogen only. Hydrocarbons
• recognise and write structures play a key role in our daily life. You must be familiar
of isomers of alkanes,
with the terms ‘LPG’ and ‘CNG’ used as fuels. LPG is the
alkenes, alkynes and aromatic
abbreviated form of liquified petroleum gas whereas CNG
hydrocarbons;
• learn about various methods of
stands for compressed natural gas. Another term ‘LNG’
preparation of hydrocarbons; (liquified natural gas) is also in news these days. This is
• distinguish between alkanes, also a fuel and is obtained by liquifaction of natural gas.
alkenes, alkynes and aromatic Petrol, diesel and kerosene oil are obtained by the fractional
hydrocarbons on the basis of distillation of petroleum found under the earth’s crust.
physical and chemical properties; Coal gas is obtained by the destructive distillation of
• draw and differentiate between coal. Natural gas is found in upper strata during drilling
various conformations of ethane; of oil wells. The gas after compression is known as
• appreciate the role of compressed natural gas. LPG is used as a domestic fuel
hydrocarbons as sources of
with the least pollution. Kerosene oil is also used as a
energy and for other industrial
applications;
domestic fuel but it causes some pollution. Automobiles
• predict the formation of need fuels like petrol, diesel and CNG. Petrol and CNG
the addition products of operated automobiles cause less pollution. All these fuels
unsymmetrical alkenes and contain mixture of hydrocarbons, which are sources of
alkynes on the basis of electronic energy. Hydrocarbons are also used for the manufacture
mechanism; of polymers like polythene, polypropene, polystyrene etc.
• comprehend the structure of Higher hydrocarbons are used as solvents for paints. They
benzene, explain aromaticity are also used as the starting materials for manufacture
and understand mechanism of many dyes and drugs. Thus, you can well understand
of electrophilic substitution
the importance of hydrocarbons in your daily life. In this
reactions of benzene;
• predict the directive influence of
unit, you will learn more about hydrocarbons.
substituents in monosubstituted
9.1 CLASSIFICATION
benzene ring;
• learn about carcinogenicity and Hydrocarbons are of different types. Depending upon
toxicity. the types of carbon-carbon bonds present, they can
be classified into three main categories – (i) saturated

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 296 chemistry

(ii) unsaturated and (iii) aromatic of the general formula for alkane family
hydrocarbons. Saturated hydrocarbons or homologous series? If we examine the
contain carbon-carbon and carbon-hydrogen formula of different alkanes we find that
single bonds. If different carbon atoms are the general formula for alkanes is CnH2n+2. It
joined together to form open chain of carbon represents any particular homologue when n
atoms with single bonds, they are termed is given appropriate value. Can you recall the
as alkanes as you have already studied in structure of methane? According to VSEPR
Unit 8. On the other hand, if carbon atoms theory (Unit 4), methane has a tetrahedral
form a closed chain or a ring, they are termed structure (Fig. 9.1), in which carbon atom lies
as cycloalkanes. Unsaturated hydrocarbons at the centre and the four hydrogen atoms lie
contain carbon-carbon multiple bonds – at the four corners of a regular tetrahedron.
double bonds, triple bonds or both. Aromatic All H-C-H bond angles are of 109.5°.
hydrocarbons are a special type of cyclic
compounds. You can construct a large
number of models of such molecules of both
types (open chain and close chain) keeping
in mind that carbon is tetravalent and
hydrogen is monovalent. For making models
of alkanes, you can use toothpicks for bonds
and plasticine balls for atoms. For alkenes,
alkynes and aromatic hydrocarbons, spring
models can be constructed. Fig. 9.1 Structure of methane
In alkanes, tetrahedra are joined together
9.2 ALKANES
in which C-C and C-H bond lengths are
As already mentioned, alkanes are saturated
154 pm and 112 pm respectively (Unit 8).
open chain hydr ocarbons containing
You have already read that C–C and C–H σ
carbon - carbon single bonds. Methane (CH4)
bonds are formed by head-on overlapping of
is the first member of this family. Methane is 3
sp hybrid orbitals of carbon and 1s orbitals
a gas found in coal mines and marshy places.
of hydrogen atoms.
If you replace one hydrogen atom of methane
by carbon and join the required number of 9.2.1 Nomenclature and Isomerism
hydrogens to satisfy the tetravalence of the You have already read about nomenclature
other carbon atom, what do you get? You of different classes of organic compounds
get C2H6. This hydrocarbon with molecular in Unit 8. Nomenclature and isomerism
formula C2H6 is known as ethane. Thus you in alkanes can further be understood with
can consider C2H6 as derived from CH4 by the help of a few more examples. Common
replacing one hydrogen atom by -CH3 group. names are given in parenthesis. First three
Go on constructing alkanes by doing this alkanes – methane, ethane and propane have
theoretical exercise i.e., replacing hydrogen only one structure but higher alkanes can
atom by –CH3 group. The next molecules will have more than one structure. Let us write
be C3H8, C4H10 … structures for C4H10. Four carbon atoms of
H H H C4H10 can be joined either in a continuous
replace any H by - CH3 chain or with a branched chain in the
H—C—H H—C—C—H or C2H6
following two ways :
H H H I
These hydrocarbons are inert under
normal conditions as they do not react with
acids, bases and other reagents. Hence,
they were earlier known as paraffins (latin :
parum, little; affinis, affinity). Can you think Butane (n- butane), (b.p. 273 K)

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 Hydrocarbons 297

II isomers. It is also clear that structures I and

III have continuous chain of carbon atoms
but structures II, IV and V have a branched
chain. Such structural isomers which differ
in chain of carbon atoms are known as chain
isomers. Thus, you have seen that C4H10
2-Methylpropane (isobutane) and C5H12 have two and three chain isomers
(b.p.261 K) respectively.
In how many ways, you can join five Problem 9.1
carbon atoms and twelve hydrogen atoms of Write structures of different chain
C5H12? They can be arranged in three ways isomers of alkanes corresponding to the
as shown in structures III–V molecular formula C6H14. Also write their
III IUPAC names.

Solution
(i) CH3 – CH2 – CH2 – CH2– CH2– CH3
n-Hexane
Pentane (n-pentane)
(b.p. 309 K)

IV
2-Methylpentane

3-Methylpentane

2-Methylbutane (isopentane)
(b.p. 301 K)
2,3-Dimethylbutane
V

2,2 - Dimethylbutane

Based upon the number of carbon atoms

attached to a carbon atom, the carbon atom is
2,2-Dimethylpropane (neopentane) termed as primary (1°), secondary (2°), tertiary
(b.p. 282.5 K) (3°) or quaternary (4°). Carbon atom attached
Structures I and II possess same molecular to no other carbon atom as in methane or to
formula but differ in their boiling points and only one carbon atom as in ethane is called
other properties. Similarly structures III, IV primary carbon atom. Terminal carbon
and V possess the same molecular formula atoms are always primary. Carbon atom
but have different properties. Structures I and attached to two carbon atoms is known as
II are isomers of butane, whereas structures secondary. Tertiary carbon is attached to
III, IV and V are isomers of pentane. Since three carbon atoms and neo or quaternary
difference in properties is due to difference in carbon is attached to four carbon atoms. Can
their structures, they are known as structural you identify 1°, 2°, 3° and 4° carbon atoms in

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 298 chemistry

structures I to V ? If you go on constructing compounds. These groups or substituents

structures for higher alkanes, you will be are known as alkyl groups as they are derived
getting still larger number of isomers. C6H14 from alkanes by removal of one hydrogen
has got five isomers and C7H16 has nine. As atom. General formula for alkyl groups is
many as 75 isomers are possible for C10H22. CnH2n+1 (Unit 8).
In structures II, IV and V, you observed Let us recall the general rules for
that –CH3 group is attached to carbon atom nomenclature already discussed in Unit 8.
numbered as 2. You will come across groups Nomenclature of substituted alkanes can
like –CH 3, –C 2H 5, –C 3H 7 etc. attached to further be understood by considering the
carbon atoms in alkanes or other classes of following problem:

Problem 9.2
Write structures of different isomeric alkyl groups corresponding to the molecular formula
C5H11. Write IUPAC names of alcohols obtained by attachment of –OH groups at different
carbons of the chain.
Solution
Structures of – C5H11 group Corresponding alcohols Name of alcohol

(i) CH3 – CH2 – CH2 – CH2– CH2 – CH3 – CH2 – CH2 – CH2– CH2 – OH Pentan-1-ol

(ii) CH3 – CH – CH2 – CH2 – CH3 CH3 – CH – CH2 – CH2– CH3 Pentan-2-ol
| |
OH

(iii) CH3 – CH2 – CH – CH2 – CH3 CH3 – CH2 – CH – CH2– CH3 Pentan-3-ol
| |
OH

CH3 CH3 3-Methyl-

| | butan-1-ol
(iv) CH3 – CH – CH2 – CH2 – CH3 – CH – CH2 – CH2– OH

CH3 CH3 2-Methyl-

| | butan-1-ol
(v) CH3 – CH2 – CH – CH2 – CH3 – CH2 – CH – CH2– OH

CH3 CH3 2-Methyl-

| | butan-2-ol
(vi) CH3 – C – CH2 – CH3 CH3 – C – CH2 – CH3
| |
OH
CH3 CH3 2,2- Dimethyl-
| | propan-1-ol
(vii) CH3 – C – CH2 – CH3 – C – CH2OH
| |
CH3 CH3

CH3 CH3 OH 3-Methyl-

| | | | butan-2-ol
(viii) CH3 – CH – CH –CH3 CH3 – CH – CH –CH3

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Table 9.1 Nomenclature of a Few Organic Compounds

Structure and IUPAC Name Remarks

Lowest sum and

1 2 3 4 5 6
(a) CH3– CH – CH2 – CH – CH2 – CH3 alphabetical
(4 – Ethyl – 2 – methylhexane) arrangement

Lowest sum and

8 7 6 5 4 3 2 1
(b) CH3 – CH2 – CH2 – CH – CH – C – CH2 – CH3 alphabetical
arrangement

(3,3-Diethyl-5-isopropyl-4-methyloctane)

1 2 3 4 5 6 7 8 9 10 sec is not considered

(c) CH3– CH2– CH2– CH– CH– CH2– CH2– CH2– CH2– CH3 while arranging
alphabetically;
isopropyl is taken
5-sec– Butyl-4-isopropyldecane
as one word
1 2 3 4 5 6 7 8 9
(d) CH3– CH2– CH2– CH2– CH– CH2– CH2– CH2– CH3
Further numbering
to the substituents
of the side chain

5-(2,2– Dimethylpropyl)nonane
1 2 3 4 5 6 7
(e) CH3 – CH2 – CH – CH2 – CH – CH2 – CH3
Alphabetical
priority order
3–Ethyl–5–methylheptane

Problem 9.3 important to write the correct structure

from the given IUPAC name. To do this, first
Write IUPAC names of the following
of all, the longest chain of carbon atoms
compounds :
corresponding to the parent alkane is written.
(i) (CH3)3 C CH2C(CH3)3 Then after numbering it, the substituents are
(ii) (CH3)2 C(C2H5)2 attached to the correct carbon atoms and
(iii) tetra – tert-butylmethane finally valence of each carbon atom is satisfied
by putting the correct number of hydrogen
Solution atoms. This can be clarified by writing the
(i) 2, 2, 4, 4-Tetramethylpentane structure of 3-ethyl-2, 2–dimethylpentane in
(ii) 3, 3-Dimethylpentane the following steps :
(iii) 3,3-Di-tert-butyl -2, 2, 4, 4 - i) Draw the chain of five carbon atoms:
tetramethylpentane C–C–C–C–C
If it is important to write the correct ii) Give number to carbon atoms:
1 2 3 4 5
IUPAC name for a given structure, it is equally C –C –C –C –C

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 300 chemistry

iii) Attach ethyl group at carbon 3 and two Longest chain is of six carbon atoms and
methyl groups at carbon 2 not that of five. Hence, correct name is
3-Methylhexane.
7 6 5 4 3 2 1
1 2 3 4 5
C – C– C– C– C
(ii) CH3 – CH2 – CH – CH2 – CH – CH2 – CH3

iv) Satisfy the valence of each carbon atom

by putting requisite number of hydrogen Numbering is to be started from the
atoms : end which gives lower number to ethyl
group. Hence, correct name is 3-ethyl-5-
methylheptane.
CH3 – C – CH – CH2 – CH3
9.2.2 Preparation

Petroleum and natural gas are the main
Thus we arrive at the correct structure. sources of alkanes. However, alkanes can be
If you have understood writing of structure prepared by following methods :
from the given name, attempt the following
problems. 1. From unsaturated hydrocarbons
Dihydrogen gas adds to alkenes and alkynes
Problem 9.4 in the presence of finely divided catalysts like
Write structural formulas of the following platinum, palladium or nickel to form alkanes.
compounds : This process is called hydrogenation. These
(i) 3, 4, 4, 5–Tetramethylheptane metals adsorb dihydrogen gas on their
surfaces and activate the hydrogen – hydrogen
(ii) 2,5-Dimethyhexane bond. Platinum and palladium catalyse the
Solution reaction at room temperature but relatively
higher temperature and pressure are required
with nickel catalysts.
(i) CH3 – CH2 – CH – C – CH– CH – Pt/Pd/Ni
CH 2 =CH 2 + H 2 CH 3 −CH 3
CH3
EthenePropane (9.1)
Pt/Pd/Ni
CH 2–CH=CH 2 + H 2 CH 3−CH 2CH 3
PropanePropane
   
(ii) CH3 – CH – CH2 – CH2 – CH – CH3 (9.2)
Pt/Pd/Ni
Problem 9.5 CH 3–C≡ C–H + 2H CH 3−CH 2CH 3
Wr it e structur es for each of th e PropynePropane
following compounds. Why are the given
(9.3)
names incorrect? Write correct IUPAC
names.
2. From alkyl halides
(i) 2-Ethylpentane
i) Alkyl halides (except fluorides) on reduction
(ii) 5-Ethyl – 3-methylheptane with zinc and dilute hydrochloric acid give
Solution alkanes.
(i) CH3 – CH – CH2– CH2 – CH3 +
Zn,H
CH–C1+H2 CH4+HC1 (9.4)

Chloromethane Methane

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C2H5–C1+H2 Zn,H
+
C2H6+HC1 alkane containing even number of
Chloroethane Ethane (9.5) carbon atoms at the anode.
− +
2CH3COO Na + 2H2O
CH3CH2CH3+CH1
+
CH3CH2CH2C1 + H2 Zn,H

1-Chloropropane Propane Sodium acetate

(9.6) ↓ Electrolysts
ii) Alkyl halides on treatment with sodium CH3 − CH3 + 2CO2 + H2 + 2NaOH
(9.9)
metal in dry ethereal (free from moisture)
solution give higher alkanes. This reaction The reaction is supposed to follow the
is known as Wurtz reaction and is used following path :
O
for the preparation of higher alkanes
– + – +
containing even number of carbon i) 2CH3COO Na 2CH3 – C – O +2Na
atoms.
ii) At anode:
CH3Br+2Na+BrCH3 dry ether CH3+2Na
O O
Bromomenthane Ethane – –02e– .
(9.7) 2CH3 –C–O 2CH3 – C – 2CH3+2CO2↑
C2H5br+2Na+BrC2H5 dry ether C2H5–C2H Acetate ion Acetate Methyl free
free radical radical
Bromoethane n–Butane iii) H3C + CH3 H3C–CH3↑
(9.8) iv) At cathode :
What will happen if two different alkyl halides
are taken? H2O+e–→–OH+
2 →H2↑
3. From carboxylic acids
i) Sodium salts of carboxylic acids on Methane cannot be prepared by this
heating with soda lime (mixture of sodium method. Why?
hydroxide and calcium oxide) give alkanes
9.2.3 Properties
containing one carbon atom less than the
carboxylic acid. This process of elimination Physical properties
of carbon dioxide from a carboxylic acid is Alkanes are almost non-polar molecules
known as decarboxylation. because of the covalent nature of C-C and
– + CaO
C-H bonds and due to very little difference
CH3COO Na +MaOH ∆ CH4+NaCO3 of electronegativity between carbon and
Sodium ethanoate hydrogen atoms. They possess weak van der
Waals forces. Due to the weak forces, the first
Problem 9.6 four members, C1 to C4 are gases, C5 to C17
Sodium salt of which acid will be needed are liquids and those containing 18 carbon
for the preparation of propane ? Write atoms or more are solids at 298 K. They are
chemical equation for the reaction. colourless and odourless. What do you think
about solubility of alkanes in water based
Solution upon non-polar nature of alkanes? Petrol
Butanoic acid, is a mixture of hydrocarbons and is used
– +
CH3CH2CH2COO Na + NaOH CaO as a fuel for automobiles. Petrol and lower
fractions of petroleum are also used for dry
CH3CH2CH3+Na2CO3 cleaning of clothes to remove grease stains.
On the basis of this observation, what do
you think about the nature of the greasy
ii) Kolbe’s electrolytic method An aqueous substance? You are correct if you say that
solution of sodium or potassium salt of grease (mixture of higher alkanes) is non-
a carboxylic acid on electrolysis gives

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 302 chemistry

polar and, hence, hydrophobic in nature. It is reducing agents. However, they undergo
generally observed that in relation to solubility the following reactions under certain
of substances in solvents, polar substances conditions.
are soluble in polar solvents, whereas the
1. Substitution reactions
non-polar ones in non-polar solvents i.e., like
dissolves like. One or more hydrogen atoms of alkanes
can be replaced by halogens, nitro group
Boiling point (b.p.) of different alkanes are
and sulphonic acid group. Halogenation
given in Table 9.2 from which it is clear that
there is a steady increase in boiling point with takes place either at higher temperature
increase in molecular mass. This is due to the (573-773 K) or in the presence of diffused
fact that the intermolecular van der Waals sunlight or ultraviolet light. Lower alkanes
forces increase with increase of the molecular do not undergo nitration and sulphonation
size or the surface area of the molecule. reactions. These reactions in which hydrogen
atoms of alkanes are substituted are known
You can make an interesting observation
as substitution reactions. As an example,
by having a look on the boiling points of
three isomeric pentanes viz., (pentane, chlorination of methane is given below:
2-methylbutane and 2,2-dimethylpropane). It Halogenation
is observed (Table 9.2) that pentane having hv
a continuous chain of five carbon atoms has CH2 + C1 CH3C1 + HC1
the highest boiling point (309.1K) whereas Chloromethane (9.10)
2,2 – dimethylpropane boils at 282.5K. With
increase in number of branched chains, CH3C1 + hv
CH2 C12 + HC1
the molecule attains the shape of a sphere.
Dichloromethane (9.11)
This results in smaller area of contact and
therefore weak intermolecular forces between CH2C12 hv
CHC13 + HC1
spherical molecules, which are overcome at
Trichloromethane (9.12)
relatively lower temperatures.
hv
Chemical properties CHC13 + C12 CC14 + HC1
As already mentioned, alkanes are generally Tetrachloromethane (9.13)
inert towards acids, bases, oxidising and
Table 9.2 Variation of Melting Point and Boiling Point in Alkanes

Molecular Name Molecular b.p./(K) m.p./(K)

formula mass/u
CH4 Methane 16 111.0 90.5
C2H6 Ethane 30 184.4 101.0
C3H8 Propane 44 230.9 85.3
C4H10 Butane 58 272.4 134.6
C4H10 2-Methylpropane 58 261.0 114.7
C5H12 Pentane 72 309.1 143.3
C5H12 2-Methylbutane 72 300.9 113.1
C5H12 2,2-Dimethylpropane 72 282.5 256.4
C6H14 Hexane 86 341.9 178.5
C7H16 Heptane 100 371.4 182.4
C8H18 Octane 114 398.7 216.2
C9H20 Nonane 128 423.8 222.0
C10H22 Decane 142 447.1 243.3
C20H42 Eicosane 282 615.0 236.2

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 Hydrocarbons 303

hv steps are possible and may occur. Two such

CH3–CH3 + C12 CH3–CH2C1 + HC1
Chloroethane (9.14) steps given below explain how more highly
haloginated products are formed.
It is found that the rate of reaction of . .
alkanes with halogens is F2 > Cl2 > Br2 > I2. CH3C1 + C  1 → C  H2C1 + HC1
. .
Rate of replacement of hydrogens of alkanes is : C  H2C1 + C1– C1 → CH2C12 + C  1
3° > 2° > 1°. Fluorination is too violent to
be controlled. Iodination is very slow and a (iii) Termination: The reaction stops after
reversible reaction. It can be carried out in the some time due to consumption of reactants
presence of oxidizing agents like HIO3 or HNO3. and / or due to the following side reactions :
The possible chain terminating steps are:
CH4+I2 CH3I+HI(9.15) . .
(a) C  1 + C  1 → C1–C1
HIO3+5HI→312+3H2O(9.16) . .
(b) H3 C   + C   H3 → H3C– CH3
. .
Halogenation is supposed to proceed via (c) H3 C  1 + C  1 → H3C–C1
free radical chain mechanism involving three
Though in (c), CH3 – Cl, the one of the
steps namely initiation, propagation and
products is formed but free radicals are
termination as given below:
consumed and the chain is terminated. The
Mechanism above mechanism helps us to understand
(i) Initiation : The reaction is initiated the reason for the formation of ethane as a
by homolysis of chlorine molecule in the byproduct during chlorination of methane.
presence of light or heat. The Cl–Cl bond 2. Combustion
is weaker than the C–C and C–H bond and
Alkanes on heating in the presence of air or
hence, is easiest to break. dioxygen are completely oxidized to carbon
hv
. dioxide and water with the evolution of large
C1–C1 homolysis C H3 + C1 amount of heat.
Chlorine free radicals CH4 (g) + 202 (g) → CO2 (g) + 2H2O(1);
(ii) Propagation : Chlorine free radical Äc Hè − 890kJ mol-1
attacks the methane molecule and takes the (9.17)
reaction in the forward direction by breaking
C4H10 (g) + 13/2O2 (g) → 4CO2 (g) + 5H2O(1)
the C-H bond to generate methyl free radical
with the formation of H-Cl. Äc Hè = −2875.84kJ mol-1
+
(a) CH4 + C1 hv +
C H3 + H–C1 (9.18)
The general combustion equation for any
The methyl radical thus obtained attacks alkane is :
the second molecule of chlorine to form  3n + 1
CnH2n+2 +  O → nCO2 + (n + 1)H2O
CH3 – Cl with the liberation of another chlorine  2  2
free radical by homolysis of chlorine molecule. (9.19)
(b) CH3 + C1–C1 hv
CH3 – C1 + C1 Due to the evolution of large amount of
heat during combustion, alkanes are used as
The chlorine and methyl free radicals fuels.
generated above repeat steps (a) and (b) During incomplete combustion of alkanes
respectively and thereby setup a chain of with insufficient amount of air or dioxygen,
reactions. The propagation steps (a) and carbon black is formed which is used in
(b) are those which directly give principal the manufacture of ink, printer ink, black
products, but many other propagation pigments and as filters.

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 304 chemistry

CH4(g) + O2(g)
incomplete
C(s)+2H2 O(1) pressure in the presence of oxides of vanadium,
combustion
molybdenum or chromium supported over
(9.20)
alumina get dehydrogenated and cyclised to
3. Controlled oxidation benzene and its homologues. This reaction is
Alkanes on heating with a regulated supply known as aromatization or reforming.
of dioxygen or air at high pressure and in the
presence of suitable catalysts give a variety of
oxidation products.
3
(i) 2CH4 + O2 Cu/523K/100atm 2CH OH
Methanol
(9.21)
Mo2O3 (9.26)
(ii) CH4 + O2 HCHO + H2O
∆ Toluene (C 7H8) is methyl derivative of
Methanal
benzene. Which alkane do you suggest for
preparation of toluene ?
(9.22)
(CH3COO)Mn 6. Reaction with steam
(iii) 2CH3CH3 + 3O2 2CH3COOH
∆ Methane reacts with steam at 1273 K in the
 Ethanoic acid presence of nickel catalyst to form carbon
 + 2H2O monoxide and dihydrogen. This method is
(9.23) used for industrial preparation of dihydrogen
(iv) Ordinarily alkanes resist oxidation but gas
alkanes having tertiary H atom can be Ni
oxidized to corresponding alcohols by CH4 + H2IO CO + 3H2(9.27)
∆
potassium permanganate.
KMnO4 7. Pyrolysis
(iCH3)3 CH Oxidation (CH3)3 COH Higher alkanes on heating to higher
2-Methylpropane2-Methylpropane-2-01 temperature decompose into lower alkanes,
alkenes etc. Such a decomposition reaction
(9.24) into smaller fragments by the application of
4. Isomerisation heat is called pyrolysis or cracking.
n-Alkanes on heating in the presence of
anhydrous aluminium chloride and hydrogen
chloride gas isomerise to branched chain
alkanes. Major products are given below.
Some minor products are also possible which
you can think over. Minor products are (9.28)
generally not reported in organic reactions. Pyrolysis of alkanes is believed to be a
free radical reaction. Preparation of oil gas
CH3(CH)2)4CH3 Anhy, AICI / HCI 3

or petrol gas from kerosene oil or petrol

n-Hexane involves the principle of pyrolysis. For
CH3CH–(CH2)2–CH3+CH3CH2–CH–CH2–CH3 example, dodecane, a constituent of kerosene
oil on heating to 973K in the presence of
CH3 CH3 platinum, palladium or nickel gives a mixture
2-Methylpen tane 3-Methylpenatone of heptane and pentene.
(9.25)

5. Aromatization C12H26 Pt/Pd/Ni

973K C7H16 + C5H10 Other
Products
n-Alkanes having six or more carbon atoms Dodecane Heptane Pentene
on heating to 773K at 10-20 atmospheric (9.29)

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9.2.4 Conformations 1. Sawhorse projections

Alkanes contain carbon-carbon sigma (σ) In this projection, the molecule is viewed
bonds. Electron distribution of the sigma along the molecular axis. It is then projected
molecular orbital is symmetrical around the on paper by drawing the central C–C bond
internuclear axis of the C–C bond which is as a somewhat longer straight line. Upper
not disturbed due to rotation about its axis. end of the line is slightly tilted towards
This permits free rotation about C–C single right or left hand side. The front carbon is
bond. This rotation results into different shown at the lower end of the line, whereas
spatial arrangements of atoms in space the rear carbon is shown at the upper end.
which can change into one another. Such Each carbon has three lines attached to it
spatial arrangements of atoms which can corresponding to three hydrogen atoms.
be converted into one another by rotation The lines are inclined at an angle of 120° to
around a C-C single bond are called each other. Sawhorse projections of eclipsed
conformations or conformers or rotamers. and staggered conformations of ethane are
Alkanes can thus have infinite number of depicted in Fig. 9.2.
conformations by rotation around C-C single
bonds. However, it may be remembered that
rotation around a C-C single bond is not
completely free. It is hindered by a small
–1
energy barrier of 1-20 kJ mol due to weak
repulsive interaction between the adjacent
bonds. Such a type of repulsive interaction
is called torsional strain.
Conformations of ethane : Ethane Fig. 9.2 Sawhorse projections of ethane
molecule (C2H6) contains a carbon – carbon
single bond with each carbon atom attached 2. Newman projections
to three hydrogen atoms. Considering the In this projection, the molecule is viewed at the
ball and stick model of ethane, keep one C–C bond head on. The carbon atom nearer
carbon atom stationary and rotate the other to the eye is represented by a point. Three
carbon atom around the C-C axis. This hydrogen atoms attached to the front carbon
rotation results into infinite number of spatial atom are shown by three lines drawn at an
arrangements of hydrogen atoms attached to angle of 120° to each other. The rear carbon
one carbon atom with respect to the hydrogen atom (the carbon atom away from the eye) is
atoms attached to the other carbon atom. represented by a circle and the three hydrogen
These are called conformational isomers atoms are shown attached to it by the shorter
(conformers). Thus there are infinite number lines drawn at an angle of 120° to each other.
of conformations of ethane. However, there are The Newman’s projections are depicted in
two extreme cases. One such conformation Fig. 9.3.
in which hydrogen atoms attached to two
carbons are as closed together as possible is
called eclipsed conformation and the other in
which hydrogens are as far apart as possible
is known as the staggered conformation. Any
other intermediate conformation is called a
skew [Link] may be remembered
that in all the conformations, the bond angles
and the bond lengths remain the same.
Eclipsed and the staggered conformations can
be represented by Sawhorse and Newman
projections.
Fig. 9.3 Newman’s projections of ethane

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 306 chemistry

Relative stability of conformations: As the first member, ethylene or ethene (C2H4)

mentioned earlier, in staggered form of ethane, was found to form an oily liquid on reaction
the electron clouds of carbon-hydrogen bonds with chlorine.
are as far apart as possible. Thus, there are
9.3.1 Structure of Double Bond
minimum repulsive forces, minimum energy
and maximum stability of the molecule. On the Carbon-carbon double bond in alkenes
other hand, when the staggered form changes consists of one strong sigma (σ) bond (bond
–1
into the eclipsed form, the electron clouds of the enthalpy about 397 kJ mol ) due to head-on
2
carbon – hydrogen bonds come closer to each overlapping of sp hybridised orbitals and
other resulting in increase in electron cloud one weak pi (π) bond (bond enthalpy about
–1
repulsions. To check the increased repulsive 284 kJ mol ) obtained by lateral or sideways
forces, molecule will have to possess more overlapping of the two 2p orbitals of the two
energy and thus has lesser stability. As already carbon atoms. The double bond is shorter in
mentioned, the repulsive interaction between bond length (134 pm) than the C–C single
the electron clouds, which affects stability of bond (154 pm). You have already read that
a conformation, is called torsional strain. the pi (π) bond is a weaker bond due to poor
Magnitude of torsional strain depends upon sideways overlapping between the two 2p
the angle of rotation about C–C bond. This orbitals. Thus, the presence of the pi (π) bond
angle is also called dihedral angle or torsional makes alkenes behave as sources of loosely
angle. Of all the conformations of ethane, the held mobile electrons. Therefore, alkenes are
easily attacked by reagents or compounds
staggered form has the least torsional strain
which are in search of electrons. Such
and the eclipsed form, the maximum torsional
reagents are called electrophilic reagents.
strain. Therefore, staggered conformation is
The presence of weaker π-bond makes alkenes
more stable than the eclipsed conformation.
unstable molecules in comparison to alkanes
Hence, molecule largely remains in staggered
and thus, alkenes can be changed into single
conformation or we can say that it is preferred
bond compounds by combining with the
conformation. Thus it may be inferred that
electrophilic reagents. Strength of the double
rotation around C–C bond in ethane is not –1
bond (bond enthalpy, 681 kJ mol ) is greater
completely free. The energy difference between
than that of a carbon-carbon single bond in
the two extreme forms is of the order of 12.5 –1
–1 ethane (bond enthalpy, 348 kJ mol ). Orbital
kJ mol , which is very small. Even at ordinary
diagrams of ethene molecule are shown in
temperatures, the ethane molecule gains
Figs. 9.4 and 9.5.
thermal or kinetic energy sufficient enough to
–1
overcome this energy barrier of 12.5 kJ mol
through intermolecular collisions. Thus, it
can be said that rotation about carbon-carbon
single bond in ethane is almost free for all
practical purposes. It has not been possible to
separate and isolate different conformational
isomers of ethane.

9.3 Alkenes
Alkenes are unsaturated hydrocarbons
Fig. 9.4 Orbital picture of ethene depicting
containing at least one double bond. What
σ bonds only
should be the general formula of alkenes? If
there is one double bond between two carbon 9.3.2 Nomenclature
atoms in alkenes, they must possess two For nomenclature of alkenes in IUPAC system,
hydrogen atoms less than alkanes. Hence, the longest chain of carbon atoms containing
general formula for alkenes is CnH2n. Alkenes the double bond is selected. Numbering of the
are also known as olefins (oil forming) since chain is done from the end which is nearer to

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Fig. 9.5 Orbital picture of ethene showing formation of (a) π-bond, (b) π-cloud and (c) bond angles and
bond lengths

the double bond. The suffix ‘ene’ replaces ‘ane’

of alkanes. It may be remembered that first Solution
member of alkene series is: CH2 (replacing (i) 2,8-Dimethyl-3, 6-decadiene;
n by 1 in CnH2n) known as methene but has (ii) 1,3,5,7 Octatetraene;
a very short life. As already mentioned, first
(iii) 2-n-Propylpent-1-ene;
stable member of alkene series is C2H4 known
as ethylene (common) or ethene (IUPAC). (iv) 4-Ethyl-2,6-dimethyl-dec-4-ene;
IUPAC names of a few members of alkenes
Problem 9.8
are given below :
Calculate number of sigma (σ) and pi (π)
Structure IUPAC name
bonds in the above structures (i-iv).
CH3 – CH = CH2 Propene
CH3 – CH2 – CH = CH2 But – l - ene Solution
CH3 – CH = CH–CH3 But-2-ene σ bonds : 33, π bonds : 2
CH2 = CH – CH = CH2 Buta – 1,3 - diene σ bonds : 17, π bonds : 4
CH2 = C – CH3 2-Methylprop-1-ene σ bonds : 23, π bond : 1
| σ bonds : 41, π bond : 1
CH3
CH2 = CH – CH – CH3 3-Methylbut-1-ene 9.3.3 Isomerism
|
CH3 Alkenes show both structural isomerism and
geometrical isomerism.
Structural isomerism : As in alkanes, ethene
Problem 9.7
(C2H4) and propene (C3H6) can have only one
Write IUPAC names of the following
structure but alkenes higher than propene
compounds:
have different structures. Alkenes possessing
(i) (CH3)2CH – CH = CH – CH2 – CH C4H8 as molecular formula can be written in

the following three ways:
CH3 – CH – CH
| I. 1 2 3 4
C2H5 CH2 = CH – CH2 – CH3

(ii) But-1-ene
(C4H8)
(iii) CH2 = C (CH2CH2CH3)2
(iv) CH3 CH2 CH2 CH2 CH2CH3 II. 1 2 3 4
| | CH3 – CH = CH – CH3
CH3 – CHCH = C – CH2 – CHCH3
| But-2-ene
CH3 (C4H8)

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 308 chemistry

III. 1 2 3 In (a), the two identical atoms i.e., both

CH2 = C – CH3 the X or both the Y lie on the same side
| of the double bond but in (b) the two X or
CH3 two Y lie across the double bond or on the
2-Methyprop-1-ene opposite sides of the double bond. This
(C4H8) results in different geometry of (a) and (b) i.e.
disposition of atoms or groups in space in
Structures I and III, and II and III are
the two arrangements is different. Therefore,
the examples of chain isomerism whereas
they are stereoisomers. They would have the
structures I and II are position isomers.
same geometry if atoms or groups around
Problem 9.9 C=C bond can be rotated but rotation around
C=C bond is not free. It is restricted. For
Write structures and IUPAC names of
understanding this concept, take two pieces
different structural isomers of alkenes
of strong cardboards and join them with the
corresponding to C5H10.
help of two nails. Hold one cardboard in your
Solution one hand and try to rotate the other. Can
(a) CH2 = CH – CH2 – CH2 – CH3 you really rotate the other cardboard ? The
answer is no. The rotation is restricted. This
Pent-1-ene
illustrates that the restricted rotation of atoms
(b) CH3 – CH=CH – CH2 – CH3 or groups around the doubly bonded carbon
Pent-2-ene atoms gives rise to different geometries of
(c) CH3 – C = CH – CH3 such compounds. The stereoisomers of this
| type are called geometrical isomers. The
CH3 isomer of the type (a), in which two identical
2-Methylbut-2-ene atoms or groups lie on the same side of the
double bond is called cis isomer and the
(d) CH3 – CH – CH = CH2 other isomer of the type (b), in which identical
| atoms or groups lie on the opposite sides of
CH3 the double bond is called trans isomer . Thus
3-Methylbut-1-ene cis and trans isomers have the same structure
(e) CH2 = C – CH2 – CH3 but have different configuration (arrangement
| of atoms or groups in space). Due to different
CH3 arrangement of atoms or groups in space,
these isomers differ in their properties like
2-Methylbut-1-ene melting point, boiling point, dipole moment,
Geometrical isomerism: Doubly bonded solubility etc. Geometrical or cis-trans isomers
carbon atoms have to satisfy the remaining of but-2-ene are represented below :
two valences by joining with two atoms or
groups. If the two atoms or groups attached
to each carbon atom are different, they can
be represented by YX C = C XY like structure.
YX C = C XY can be represented in space in
the following two ways :

Cis form of alkene is found to be more

polar than the trans form. For example,
dipole moment of cis-but-2-ene is 0.33 Debye,
whereas, dipole moment of the trans form
is almost zero or it can be said that

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 Hydrocarbons 309

trans-but-2-ene is non-polar. This can be (ii) CH2 = CBr2

understood by drawing geometries of the two
forms as given below from which it is clear (iii) C6H5CH = CH – CH3
that in the trans-but-2-ene, the two methyl (iv) CH3CH = CCl CH3
groups are in opposite directions, Threfore,
dipole moments of C-CH3 bonds cancel, thus Solution
making the trans form non-polar. (iii) and (iv). In structures (i) and (ii), two
identical groups are attached to one of
the doubly bonded carbon atom.

9.3.4 Preparation
1. From alkynes: Alkynes on partial
reduction with calculated amount of
cis-But-2-ene trans-But-2-ene dihydrogen in the presence of palladised
(µ = 0.33D) (µ = 0) charcoal partially deactivated with poisons
In the case of solids, it is observed that the like sulphur compounds or quinoline give
trans isomer has higher melting point than alkenes. Partially deactivated palladised
the cis form. charcoal is known as Lindlar’s catalyst.
Alkenes thus obtained are having cis
Geometrical or cis-trans isomerism
geometry. However, alkynes on reduction
is also shown by alkenes of the types
XYC = CXZ and XYC = CZW with sodium in liquid ammonia form trans
alkenes.
Problem 9.10
Draw cis and trans isomers of the
following compounds. Also write their
IUPAC names :
(i) CHCl = CHCl (9.30)
(ii) C2H5CCH3 = CCH3C2H5

Solution

(9.31)
Pd/C
iii) CH≡ CH+H2 CH2 =CH2 (9.32)
Ethyne Ethene
Pd/C
CH3–C≡ CH+H2 CH3–CH =CH2
iv)
Propyne Propene
(9.33)
Wi l l p r o p e n e t h u s o b t a i n e d s h o w
Problem 9.11 geometrical isomerism? Think for the
Which of the following compounds will reason in support of your answer.
show cis-trans isomerism? 2. From alkyl halides: Alkyl halides (R-X) on
(i) (CH3)2C = CH – C2H5 heating with alcoholic potash (potassium
hydroxide dissolved in alcohol, say,

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 310 chemistry

ethanol) eliminate one molecule of halogen takes out one hydrogen atom from the
acid to form alkenes. This reaction is β-carbon atom.
known as dehydrohalogenation i.e.,
removal of halogen acid. This is example
of β-elimination reaction, since hydrogen
atom is eliminated from the β carbon atom
(carbon atom next to the carbon to which
halogen is attached).
(9.37)
9.3.5 Properties
Physical properties
Alkenes as a class resemble alkanes in
physical properties, except in types of
isomerism and difference in polar nature.
(9.34) The first three members are gases, the next
Nature of halogen atom and the alkyl fourteen are liquids and the higher ones are
group determine rate of the reaction. It solids. Ethene is a colourless gas with a faint
is observed that for halogens, the rate is: sweet smell. All other alkenes are colourless
iodine > bromine > chlorine, while for alkyl and odourless, insoluble in water but fairly
groups it is : tert > secondary > primary. soluble in non-polar solvents like benzene,
petroleum ether. They show a regular increase
3. From vicinal dihalides: Dihalides in
in boiling point with increase in size i.e., every
which two halogen atoms are attached
– CH2 group added increases boiling point by
to two adjacent carbon atoms are known
20–30 K. Like alkanes, straight chain alkenes
as vicinal dihalides. Vicinal dihalides on
have higher boiling point than isomeric
treatment with zinc metal lose a molecule
branched chain compounds.
of ZnX2 to form an alkene. This reaction
is known as dehalogenation. Chemical properties
Alkenes are the rich source of loosely held
CH2Br–CH2Br + Zn CH2=CH2+ ZnBr2 pi (π) electrons, due to which they show
(9.35) addition reactions in which the electrophiles
CH3CHBr–CH2Br + Zn CH3CH=CH2 add on to the carbon-carbon double bond to
form the addition products. Some reagents
+ZnBr2 also add by free radical mechanism. There
(9.36) are cases when under special conditions,
4. From alcohols by acidic dehydration: alkenes also undergo free radical substitution
You have read during nomenclature of reactions. Oxidation and ozonolysis reactions
different homologous series in Unit 12 are also quite prominent in alkenes. A brief
that alcohols are the hydroxy derivatives description of different reactions of alkenes
of alkanes. They are represented by R–OH is given below:
where, R is CnH2n+1. Alcohols on heating 1. Addition of dihydrogen: Alkenes add
with concentrated sulphuric acid form up one molecule of dihydrogen gas in
alkenes with the elimination of one water the presence of finely divided nickel,
molecule. Since a water molecule is palladium or platinum to form alkanes
eliminated from the alcohol molecule in (Section 9.2.2)
the presence of an acid, this reaction is 2. Addition of halogens : Halogens like
known as acidic dehydration of alcohols. bromine or chlorine add up to alkene to
This reaction is also the example of form vicinal dihalides. However, iodine
β-elimination reaction since –OH group does not show addition reaction under

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 Hydrocarbons 311

normal conditions. The reddish orange

colour of bromine solution in carbon
tetrachloride is discharged when bromine
adds up to an unsaturation site. This
reaction is used as a test for unsaturation.
Addition of halogens to alkenes is an
example of electrophilic addition reaction
involving cyclic halonium ion formation (9.42)
which you will study in higher classes. Markovnikov, a Russian chemist made a
generalisation in 1869 after studying such
reactions in detail. These generalisations
led Markovnikov to frame a rule called
Markovnikov rule. The rule states that
negative part of the addendum (adding
(9.38) molecule) gets attached to that carbon atom
which possesses lesser number of hydrogen
atoms. Thus according to this rule, product
I i.e., 2-bromopropane is expected. In actual
practice, this is the principal product of the
reaction. This generalisation of Markovnikov
(9.39) rule can be better understood in terms of
mechanism of the reaction.
3. Addition of hydrogen halides: Hydrogen
halides (HCl, HBr,HI) add up to alkenes Mechanism
to for m alkyl halides. The order of Hydrogen bromide provides an electrophile,
+
reactivity of the hydrogen halides is H , which attacks the double bond to form
HI > HBr > HCl. Like addition of halogens carbocation as shown below :
to alkenes, addition of hydrogen halides is
also an example of electrophilic addition
reaction. Let us illustrate this by taking
addition of HBr to symmetrical and
unsymmetrical alkenes
Addition reaction of HBr to symmetrical
alkenes
(a) less stable (b) more stable
Addition reactions of HBr to symmetrical
primary carbocation secondary carbocation
alkenes (similar groups attached to double
bond) take place by electrophilic addition (i) The secondary carbocation (b) is more
mechanism. stable than the primary carbocation
(a), therefore, the former predominates
CH2=CH2+H–Br CH3–CH2–Br (9.40)
because it is formed at a faster rate.
–
CH3–CH=CH–CH3+HBr CH3–CH–CHCH3 (ii) The carbocation (b) is attacked by Br ion
to form the product as follows :
Br
(9.41)

Addition reaction of HBr to unsymmetrical

alkenes (Markovnikov Rule)
How will H – Br add to propene ? The two 2-Bromopropane
possible products are I and II. (major product)

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 312 chemistry

Anti Markovnikov addition or peroxide

effect or Kharash effect
In the presence of peroxide, addition of HBr
to unsymmetrical alkenes like propene takes
place contrary to the Markovnikov rule. This
happens only with HBr but not with HCl
The secondary free radical obtained in the
and Hl. This addition reaction was observed
above mechanism (step iii) is more stable than
by M.S. Kharash and F.R. Mayo in 1933 the primary. This explains the formation of
at the University of Chicago. This reaction 1-bromopropane as the major product. It may
is known as peroxide or Kharash effect be noted that the peroxide effect is not observed
or addition reaction anti to Markovnikov in addition of HCl and HI. This may be due
rule. to the fact that the H–Cl bond being
–1
(C6H5CO)2O2 stronger (430.5 kJ mol ) than H–Br bond
CH3 – CH=CH2+HBr CH3–CH2 –1
(363.7 kJ mol ), is not cleaved by the free
radical, whereas the H–I bond is weaker
CH2Br –1
(296.8 kJ mol ) and iodine free radicals
1–Bromopropane combine to form iodine molecules instead of
adding to the double bond.
(9.43)

Mechanism : Peroxide effect proceeds via Problem 9.12

free radical chain mechanism as given below: Write IUPAC names of the products
obtained by addition reactions of HBr to
(i)
hex-1-ene
(i) in the absence of peroxide and
(ii) in the presence of peroxide.

Solution

. Homolysis .
(ii) C 6H5+H–Br C6H3+ B r

4. Addition of sulphuric acid : Cold

concentrated sulphuric acid adds to
alkenes in accordance with Markovnikov
rule to form alkyl hydrogen sulphate by
the electrophilic addition reaction.

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 Hydrocarbons 313

ketones and/or acids depending upon the

nature of the alkene and the experimental
conditions

(9.49)
+
KMnO4/H
CH3 – CH=CH–CH3 2CH3COOH
(9.44) But-2-ene Ethanoic acid
(9.50)
7. Ozonolysis : Ozonolysis of alkenes
involves the addition of ozone molecule to
alkene to form ozonide, and then cleavage
of the ozonide by Zn-H 2O to smaller
molecules. This reaction is highly useful
in detecting the position of the double
(9.45) bond in alkenes or other unsaturated
5. Addition of water : In the presence of a compounds.
few drops of concentrated sulphuric acid
alkenes react with water to form alcohols,
in accordance with the Markovnikov rule.

(9.51)
(9.46)
6. Oxidation: Alkenes on reaction with cold,
dilute, aqueous solution of potassium
permanganate (Baeyer’s reagent) produce
vicinal glycols. Decolorisation of KMnO4
solution is used as a test for unsaturation.

(9.52)
(9.47) 8. Polymerisation: You are familiar with
polythene bags and polythene sheets.
Polythene is obtained by the combination
of large number of ethene molecules at
high temperature, high pressure and
in the presence of a catalyst. The large
molecules thus obtained are called
(9.48) polymers. This reaction is known as
b) Acidic potassium permanganate or acidic polymerisation. The simple compounds
potassium dichromate oxidises alkenes to from which polymers are made are called

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 314 chemistry

monomers. Other alkenes also undergo are named as derivatives of the corresponding
polymerisation. alkanes replacing ‘ane’ by the suffix ‘yne’.
High temp./pressure
n(CH2 =CH2) Catalyst
—( CH2–CH2 —
) The position of the triple bond is indicated
Polythene by the first triply bonded carbon. Common
and IUPAC names of a few members of alkyne
(9.53) series are given in Table 9.2.
n(CH3 –CH=CH2)
High temp./pressure
—(CH–CH2 —
)n You have already learnt that ethyne and
Catalyst
propyne have got only one structure but
there are two possible structures for butyne –
CH3
(i) but-1-yne and (ii) but-2-yne. Since these
Polypropene two compounds differ in their structures
(9.54) due to the position of the triple bond, they
Polymers are used for the manufacture of plastic are known as position isomers. In how
bags, squeeze bottles, refrigerator dishes, toys, many ways, you can construct the structure
pipes, radio and T.V. cabinets etc. Polypropene for the next homologue i.e., the next alkyne
is used for the manufacture of milk crates, with molecular formula C5H8? Let us try to
plastic buckets and other moulded articles. arrange five carbon atoms with a continuous
Though these materials have now become chain and with a side chain. Following are the
common, excessive use of polythene and possible structures :
polypropylene is a matter of great concern for Structure IUPAC name
all of us. 1 2 3 4 5
I. HC≡ C– CH2– CH2– CH3 Pent–1-yne
9.4 Alkynes 1 2 3 4 5
Like alkenes, alkynes are also unsaturated II. H3C–C≡ C– CH2– CH3 Pent–2-yne
hydrocarbons. They contain at least one triple 4 3 2 1
bond between two carbon atoms. The number III. H3C–CH–C≡ CH 3-Methyl but–1-yne
|
of hydrogen atoms is still less in alkynes as
CH3
compared to alkenes or alkanes. Their general Structures I and II are position isomers
formula is CnH2n–2. and structures I and III or II and III are chain
The first stable member of alkyne series isomers.
is ethyne which is popularly known as
acetylene. Acetylene is used for arc welding Problem 9.13
purposes in the form of oxyacetylene flame Write structures of different isomers
th
obtained by mixing acetylene with oxygen corresponding to the 5 member of
gas. Alkynes are starting materials for a large alkyne series. Also write IUPAC names of
number of organic compounds. Hence, it all the isomers. What type of isomerism
is interesting to study this class of organic is exhibited by different pairs of isomers?
compounds.
Solution
9.4.1 Nomenclature and Isomerism th
5 member of alkyne has the molecular
In common system, alkynes are named as formula C6H10. The possible isomers are:
derivatives of acetylene. In IUPAC system, they
Table 9.2 Common and IUPAC Names of Alkynes (CnH2n–2)

Value of n Formula Structure Common name IUPAC name

2 C2H2 H-C≡CH Acetylene Ethyne
3 C3H4 CH3-C≡CH Methylacetylene Propyne
4 C4H6 CH3CH2-C≡CH Ethylacetylene But-1-yne
4 C4H6 CH3-C≡C-CH3 Dimethylacetylene But-2-yne

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 Hydrocarbons 315

(a) HC ≡ C – CH2 – CH2 – CH2 – CH3

Hex-1-yne
(b) CH3 – C ≡ C – CH2 – CH2 – CH3
Hex-2-yne
(c) CH3 – CH2 – C ≡ C – CH2– CH3
Hex-3-yne

3-Methylpent-1-yne

4-Methylpent-1-yne

4-Methylpent-2-yne
Fig. 9.6 Orbital picture of ethyne showing
(a) sigma overlaps (b) pi overlaps.

orbitals of the other carbon atom, which

undergo lateral or sideways overlapping to
3,3-Dimethylbut-1-yne form two pi (π) bonds between two carbon
atoms. Thus ethyne molecule consists of one
Position and chain isomerism shown by
C–C σ bond, two C–H σ bonds and two C–C
different pairs.
π bonds. The strength of C≡C bond (bond
-1
enthalpy 823 kJ mol ) is more than those
–1
9.4.2 Structure of Triple Bond of C=C bond (bond enthalpy 681 kJ mol )
–1
Ethyne is the simplest molecule of alkyne and C–C bond (bond enthalpy 348 kJ mol ).
series. Structure of ethyne is shown in The C≡C bond length is shorter (120 pm)
Fig. 9.6. than those of C=C (133 pm) and C–C (154
pm). Electron cloud between two carbon
Each carbon atom of ethyne has two sp
atoms is cylindrically symmetrical about the
hybridised orbitals. Carbon-carbon sigma (σ)
internuclear axis. Thus, ethyne is a linear
bond is obtained by the head-on overlapping
molecule.
of the two sp hybridised orbitals of the two
carbon atoms. The remaining sp hybridised 9.4.3 Preparation
orbital of each carbon atom undergoes
1. From calcium carbide: On industrial
overlapping along the internuclear axis with
scale, ethyne is prepared by treating
the 1s orbital of each of the two hydrogen
calcium carbide with water. Calcium
atoms for ming two C-H sigma bonds.
carbide is prepared by heating quick lime
H-C-C bond angle is of 180°. Each carbon
with coke. Quick lime can be obtained by
has two unhybridised p orbitals which are
heating limestone as shown in the following
perpendicular to each other as well as to the
reactions:
plane of the C-C sigma bond. The 2p orbitals
of one carbon atom are parallel to the 2p CaCO3 ∆ CaO + O2 (9.55)

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 316 chemistry

CaO + 3C CaC2 + CO (9.56) the sp hybridised carbon atoms whereas

2
Calcium they are attached to sp hybridised carbon
3
carbide atoms in ethene and sp hybridised carbons
in ethane. Due to the maximum percentage of
CaC2 + 2H2O Ca(OH)2 + C2H2 (9.57) s character (50%), the sp hybridised orbitals
of carbon atoms in ethyne molecules have
2. From vicinal dihalides : Vicinal dihalides
highest electronegativity; hence, these attract
on treatment with alcoholic potassium
the shared electron pair of the C-H bond of
hydroxide undergo dehydrohalogenation.
ethyne to a greater extent than that of the
One molecule of hydrogen halide is 2
sp hybridised orbitals of carbon in ethene
eliminated to form alkenyl halide which 3
and the sp hybridised orbital of carbon in
on treatment with sodamide gives alkyne.
ethane. Thus in ethyne, hydrogen atoms
can be liberated as protons more easily as
compared to ethene and ethane. Hence,
hydrogen atoms of ethyne attached to triply
bonded carbon atom are acidic in nature. You
may note that the hydrogen atoms attached
to the triply bonded carbons are acidic but
not all the hydrogen atoms of alkynes.
– +
HC ≡ CH + Na → HC ≡ C Na + 1/2 H2
9.4.4 Properties
Monosodium
Physical properties ethynide
Physical properties of alkynes follow the same
(9.59)
trend of alkenes and alkanes. First three – + – + – +
members are gases, the next eight are liquids HC ≡ C Na + Na → Na C Na ≡ C Na + 1/2 H
2
and the higher ones are solids. All alkynes Disodium ethynide
are colourless. Ethyene has characteristic
(9.60)
odour. Other members are odourless. Alkynes + –
are weakly polar in nature. They are lighter CH3 – C ≡ C – H + Na NH 2
than water and immiscible with water but ↓
– +
soluble in organic solvents like ethers, carbon CH3 – C ≡ C Na + NH3
tetrachloride and benzene. Their melting Sodium propynide (9.61)
point, boiling point and density increase with
These reactions are not shown by alkenes
increase in molar mass.
and alkanes, hence used for distinction
Chemical properties between alkynes, alkenes and alkanes. What
Alkynes show acidic nature, addition reactions about the above reactions with but-1-yne and
and polymerisation reactions as follows : but-2-yne ? Alkanes, alkenes and alkynes
A. Acidic character of alkyne: Sodium follow the following trend in their acidic
metal and sodamide (NaNH 2) are strong behaviour :
bases. They react with ethyne to form sodium
acetylide with the liberation of dihydrogen i) CH ≡ CH > H2C – CH2 > CH3 –CH3
gas. These reactions have not been observed ii) HC ≡ CH > CH3 –C≡ CH >> CH3 –C≡C–CH3
in case of ethene and ethane thus indicating
that ethyne is acidic in nature in comparison B. Addition reactions: Alkynes contain a
to ethene and ethane. Why is it so ? Has triple bond, so they add up, two molecules of
it something to do with their structures dihydrogen, halogen, hydrogen halides etc.
and the hybridisation ? You have read that Formation of the addition product takes place
hydrogen atoms in ethyne are attached to according to the following steps.

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 Hydrocarbons 317

The addition product formed depends

upon stability of vinylic cation. Addition in
unsymmetrical alkynes takes place according
to Markovnikov rule. Majority of the reactions
of alkynes are the examples of electrophilic
addition reactions. A few addition reactions
are given below: (9.66)
(i) Addition of dihydrogen (iv) Addition of water
HC≡CH+H2 Pt/Pd/Ni
[H2C = CH2] H2
CH3–CH3 Like alkanes and alkenes, alkynes are also
immiscible and do not react with water.
(9.62) However, one molecule of water adds to
Pt/Pd/Ni
alkynes on warming with mercuric sulphate
CH3–C≡CH + H2 [CH3–CH=CH2] and dilute sulphuric acid at 333 K to form
Propyne Propene carbonyl compounds.
↓H2
CH3–CH2–CH3
Propane
(9.63)
(ii) Addition of halogens

(9.67)

(9.64)
Reddish orange colour of the solution
of bromine in carbon tetrachloride is
decolourised. This is used as a test for
unsaturation.
(iii) Addition of hydrogen halides (9.68)
Two molecules of hydrogen halides (HCl, HBr, (v) Polymerisation
HI) add to alkynes to form gem dihalides (in (a) Linear polymerisation: Under suitable
which two halogens are attached to the same conditions, linear polymerisation of ethyne
carbon atom) takes place to produce polyacetylene or
H–C≡C–H+H–Br [CH2 = CH–Br]→ CHBr2 polyethyne which is a high molecular
Bromoethene weight polyene containing repeating units of
CH3 (CH = CH – CH = CH ) and can be represented
1,1-Dibromoethane as —( CH = CH – CH = CH)n— Under special
(9.65) conditions, this polymer conducts electricity.

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 318 chemistry

Thin film of polyacetylene can be used as but in a majority of reactions of aromatic

electrodes in batteries. These films are good compounds, the unsaturation of benzene ring
conductors, lighter and cheaper than the is retained. However, there are examples of
metal conductors. aromatic hydrocarbons which do not contain a
(b) Cyclic polymerisation: Ethyne on benzene ring but instead contain other highly
passing through red hot iron tube at 873K unsaturated ring. Aromatic compounds
undergoes cyclic polymerization. Three containing benzene ring are known as
molecules polymerise to form benzene, which benzenoids and those not containing a
is the starting molecule for the preparation of benzene ring are known as non-benzenoids.
derivatives of benzene, dyes, drugs and large Some examples of arenes are given
number of other organic compounds. This is below:
the best route for entering from aliphatic to
aromatic compounds as discussed below:

Benzene Toluene Naphthalene

(9.69)

Problem 9.14 Biphenyl

How will you convert ethanoic acid into
benzene? 9.5.1 Nomenclature and Isomerism
The nomenclature and isomerism of aromatic
Solution hydrocarbons has already been discussed in
Unit 8. All six hydrogen atoms in benzene
are equivalent; so it forms one and only one
type of monosubstituted product. When two
hydrogen atoms in benzene are replaced by
two similar or different monovalent atoms or
groups, three different position isomers are
possible. The 1, 2 or 1, 6 is known as the ortho
(o–), the 1, 3 or 1, 5 as meta (m–) and the 1,
4 as para (p–) disubstituted compounds. A
few examples of derivatives of benzene are
given below:

9.5 Aromatic Hydrocarbon

These hydrocarbons are also known as
‘arenes’. Since most of them possess pleasant
odour (Greek; aroma meaning pleasant
smelling), the class of compounds was Methylbenzene 1,2-Dimethylbenzene
named as ‘aromatic compounds’. Most of such
compounds were found to contain benzene (Toluene) (o-Xylene)
ring. Benzene ring is highly unsaturated

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 Hydrocarbons 319

Friedrich August Kekulé,a German chemist was born in 1829 at Darmsdt in

Germany. He became Professor in 1856 and Fellow of Royal Society in 1875. He
made major contribution to structural organic chemistry by proposing in 1858 that
carbon atoms can join to one another to form chains and later in 1865,he found
an answer to the challenging problem of benzene structure by suggesting that
these chains can close to form rings. He gave the dynamic structural formula to
benzene which forms the basis for its modern electronic structure. He described
the discovery of benzene structure later as:
FRIEDRICH
“I was sitting writing at my textbook,but the work did not progress; my thoughts
AUGUST KEKULÉ
were elsewhere. I turned my chair to the fire, and dozed. Again the atoms were
(7th September
gambolling before my eyes. This time the smaller groups kept modestly in the
1829–13th July
background. My mental eye, rendered more acute by repeated visions of this
1896)
kind, could now distinguish larger structures of manifold conformations; long
rows,sometimes more closely fitted together; all twisting and turning in snake like motion. But look! What
was that? One of the snakes had seized hold of it’s own tail, and the form whirled mockingly before my
eyes. As if by a flash of lightning I woke;.... I spent the rest of the night working out the consequences of
the hypothesis. Let us learn to dream, gentlemen, and then perhaps we shall learn the truth but let us
beware of making our dreams public before they have been approved by the waking mind.”( 1890).
One hundred years later, on the occasion of Kekulé’s centenary celebrations a group of compounds
having polybenzenoid structures have been named as Kekulenes.

was further found to produce one and only one

monosubstituted derivative which indicated
that all the six carbon and six hydrogen atoms
of benzene are identical. On the basis of this
observation August Kekulé in 1865 proposed
the following structure for benzene having
cyclic arrangement of six carbon atoms with
1,3 Dimethylbenzene 1,4-Dimethylbenzene alternate single and double bonds and one
(m-Xylene) ( p-Xylene) hydrogen atom attached to each carbon atom.
9.5.2 Structure of Benzene
Benzene was isolated by Michael Faraday
in 1825. The molecular formula of benzene,
C6H6, indicates a high degree of unsaturation.
This molecular formula did not account for
its relationship to corresponding alkanes,
alkenes and alkynes which you have studied
in earlier sections of this unit. What do you The Kekulé structure indicates
think about its possible structure? Due to the possibility of two isomeric
its unique properties and unusual stability, 1, 2-dibromobenzenes. In one of the isomers,
it took several years to assign its structure. the bromine atoms are attached to the
Benzene was found to be a stable molecule doubly bonded carbon atoms whereas in the
and found to form a triozonide which indicates other, they are attached to the singly bonded
the presence of three double bonds. Benzene carbons.

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unhybridised p orbital perpendicular to the

plane of the ring as shown below:

However, benzene was found to form only

one ortho disubstituted product. This problem
was overcome by Kekulé by suggesting the
concept of oscillating nature of double bonds
in benzene as given below.

The unhybridised p orbital of carbon atoms

are close enough to form a π bond by lateral
overlap. There are two equal possibilities of
Even with this modification, Kekulé
forming three π bonds by overlap of p orbitals
structure of benzene fails to explain unusual
of C1 –C2, C3 – C4, C5 – C6 or C2 – C3, C4 – C5,
stability and preference to substitution
C6 – C1 respectively as shown in the following
reactions than addition reactions, which
figures.
could later on be explained by resonance.
Resonance and stability of benzene
According to Valence Bond Theory, the
concept of oscillating double bonds in benzene
is now explained by resonance. Benzene is a
hybrid of various resonating structures. The
two structures, A and B given by Kekulé are
the main contributing structures. The hybrid
structure is represented by inserting a circle
or a dotted circle in the hexagon as shown
in (C). The circle represents the six electrons
which are delocalised between the six carbon Fig. 9.7 (a)
atoms of the benzene ring.

(A) (B) (C)

The orbital overlapping gives us better
picture about the structure of benzene. All
2
the six carbon atoms in benzene are sp
2
hybridized. Two sp hybrid orbitals of each
2
carbon atom overlap with sp hybrid orbitals
of adjacent carbon atoms to form six C—C
sigma bonds which are in the hexagonal
2 Fig. 9.7 (b)
plane. The remaining sp hybrid orbital of
each carbon atom overlaps with s orbital Structures shown in Fig. 9.7(a) and (b)
of a hydrogen atom to form six C—H sigma correspond to two Kekulé’s structure with
bonds. Each carbon atom is now left with one localised π bonds. The internuclear distance

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between all the carbon atoms in the ring has (i) Planarity
been determined by the X-ray diffraction to (ii) Complete delocalisation of the π electrons
be the same; there is equal probability for the in the ring
p orbital of each carbon atom to overlap with
(iii) Presence of (4n + 2) π electrons in the ring
the p orbitals of adjacent carbon atoms [Fig.
where n is an integer (n = 0, 1, 2, . . .).
9.7 (c)]. This can be represented in the form
of two doughtnuts (rings) of electron clouds This is often referred to as Hückel Rule.
[Fig. 9.7 (d)], one above and one below the Some examples of aromatic compounds are
plane of the hexagonal ring as shown below: given below:

(electron cloud)

Fig. 9.7 (c) Fig. 9.7 (d)

The six π electrons are thus delocalised
and can move freely about the six carbon
nuclei, instead of any two as shown in
Fig. 9.6 (a) or (b). The delocalised π electron cloud
is attracted more strongly by the nuclei of the
carbon atoms than the electron cloud localised
between two carbon atoms. Therefore, presence
of delocalised π electrons in benzene makes
it more stable than the hypothetical
cyclohexatriene.
X-Ray diffraction data reveals that benzene
is a planar molecule. Had any one of the above
structures of benzene (A or B) been correct,
9.5.4 Preparation of Benzene
two types of C—C bond lengths were expected.
However, X-ray data indicates that all the Benzene is commercially isolated from coal
six C—C bond lengths are of the same order tar. However, it may be prepared in the
(139 pm) which is intermediate between laboratory by the following methods.
C— C single bond (154 pm) and C—C double (i) Cyclic polymerisation of ethyne:
bond (133 pm). Thus the absence of pure (Section 9.4.4)
double bond in benzene accounts for the (ii) Decarboxylation of aromatic acids:
reluctance of benzene to show addition Sodium salt of benzoic acid on heating
reactions under normal conditions, thus with sodalime gives benzene.
explaining the unusual behaviour of benzene.
9.5.3 Aromaticity
Benzene was considered as parent ‘aromatic’
compound. Now, the name is applied to all the
ring systems whether or not having benzene (9.70)
ring, possessing following characteristics.

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 322 chemistry

(iii) Reduction of phenol: Phenol is reduced (ii) Halogenation: Arenes react with halogens
to benzene by passing its vapours over in the presence of a Lewis acid like anhydrous
heated zinc dust FeCl3, FeBr3 or AlCl3 to yield haloarenes.

(9.71) Chlorobenzene
9.5.5 Properties (9.73)
Physical properties (iii) Sulphonation: The replacement of a
Aromatic hydrocarbons are non- polar hydrogen atom by a sulphonic acid group in
molecules and are usually colourless liquids a ring is called sulphonation. It is carried out
or solids with a characteristic aroma. You are by heating benzene with fuming sulphuric
also familiar with naphthalene balls which are acid (oleum).
used in toilets and for preservation of clothes
because of unique smell of the compound
and the moth repellent property. Aromatic
hydrocarbons are immiscible with water but
are readily miscible with organic solvents.
They burn with sooty flame.
Chemical properties (9.74)
Arenes are characterised by electrophilic
substitution reactions. However, under (iv) Friedel-Crafts alkylation reaction:
special conditions they can also undergo When benzene is treated with an alkyl halide
addition and oxidation reactions. in the presence of anhydrous aluminium
chloride, alkylbenene is formed.
Electrophilic substitution reactions
The common electrophilic substitution
reactions of arenes are nitration, halogenation,
sulphonation, Friedel Craft’s alkylation and
acylation reactions in which attacking reagent
+
is an electrophile (E )
(i) Nitration: A nitro group is introduced (9.75)
into benzene ring when benzene is heated
with a mixture of concentrated nitric acid
and concentrated sulphuric acid (nitrating
mixture).
(9.76)

Why do we get isopropyl benzene on

treating benzene with 1-chloropropane
instead of n-propyl benzene?

(v) Friedel-Crafts acylation reaction: The

reaction of benzene with an acyl halide or
(9.72) acid anhydride in the presence of Lewis acids
(AlCl3) yields acyl benzene.
Nitrobenzene

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 Hydrocarbons 323

(9.77)

In the case of nitration, the electrophile,

nitronium ion, is produced by transfer of
a proton (from sulphuric acid) to nitric acid
in the following manner:
(9.78) Step I
If excess of electrophilic reagent is used,
further substitution reaction may take place
in which other hydrogen atoms of benzene Step II
ring may also be successively replaced
by the electrophile. For example, benzene
on treatment with excess of chlorine in
the presence of anhydrous AlCl 3 can be Protonated Nitronium
chlorinated to hexachlorobenzene (C6Cl6) nitric acid ion
It is interesting to note that in the process
of generation of nitronium ion, sulphuric acid
serves as an acid and nitric acid as a base.
Thus, it is a simple acid-base equilibrium.
(b) F o r m a t i o n o f C a r b o c a t i o n
(arenium ion): Attack of electrophile
results in the formation of σ-complex or
(9.79) arenium ion in which one of the carbon is sp
3

Mechanism of electrophilic substitution hybridised.

reactions:
According to experimental evidences, SE (S =
substitution; E = electrophilic) reactions are
supposed to proceed via the following three
steps:
(a) Generation of the eletrophile sigma complex (arenium ion)
(b) Formation of carbocation intermediate The arenium ion gets stabilised by
(c) Removal of proton from the carbocation resonance:
intermediate
⊕
(a) Generation of electrophile E : During
chlorination, alkylation and acylation of
benzene, anhydrous AlCl3, being a Lewis acid
⊕ ⊕
helps in generation of the elctrophile Cl , R ,
⊕
RC O (acylium ion) respectively by combining
with the attacking reagent.

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 324 chemistry

Sigma complex or arenium ion loses its chemical equation:

aromatic character because delocalisation of
3 CxHy + (x + ) O2 → x CO2 + H2O n (9.83)
electrons stops at sp hybridised carbon.
(c) Removal of proton: To restore the 9.5.6 Directive influence of a functional
aromatic character, σ -complex releases group in monosubstituted benzene
3
proton from sp hybridised carbon on attack
– When monosubstituted benzene is subjected
by [AlCl4] (in case of halogenation, alkylation
– to further substitution, three possible
and acylation) and [HSO 4 ] (in case of
disubstituted products are not formed in
nitration).
equal amounts. Two types of behaviour are
observed. Either ortho and para products or
meta product is predominantly formed. It
has also been observed that this behaviour
depends on the nature of the substituent
already present in the benzene ring and not
on the nature of the entering group. This is
known as directive influence of substituents.
Reasons for ortho/para or meta directive
nature of groups are discussed below:
Addition reactions
Ortho and para directing groups: The
Under vigorous conditions, i.e., at high
groups which direct the incoming group to
temperature and/ or pressure in the presence
ortho and para positions are called ortho and
of nickel catalyst, hydrogenation of benzene para directing groups. As an example, let us
gives cyclohexane. discuss the directive influence of phenolic
(–OH) group. Phenol is resonance hybrid of
following structures:

Cyclohexane
(9.80)
Under ultra-violet light, three chlorine
molecules add to benzene to produce benzene
hexachloride, C6H6Cl6 which is also called
gammaxane.

Benzene hexachloride,
It is clear from the above resonating
(BHC) structures that the electron density is more on
(9.81) o – and p – positions. Hence, the substitution
Combustion: When heated in air, benzene takes place mainly at these positions. However,
burns with sooty flame producing CO2 and it may be noted that –I effect of – OH group also
H2O operates due to which the electron density on
15 ortho and para positions of the benzene ring
C H6 + O2 → 6CO2 +3H2O is slightly reduced. But the overall electron
6 2 (9.82) density increases at these positions of the
General combustion reaction for any ring due to resonance. Therefore, –OH group
hydrocarbon may be given by the following activates the benzene ring for the attack by

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 Hydrocarbons 325

an electrophile. Other examples of activating In this case, the overall electron density
groups are –NH2, –NHR, –NHCOCH3, –OCH3, on benzene ring decreases making further
–CH3, –C2H5, etc. substitution difficult, therefore these groups
In the case of aryl halides, halogens are are also called ‘deactivating groups’. The
moderately deactivating. Because of their electron density on o – and p – position
strong – I effect, overall electron density on is comparatively less than that at meta
benzene ring decreases. It makes further position. Hence, the electrophile attacks on
substitution difficult. However, due to comparatively electron rich meta position
resonance the electron density on o– and resulting in meta substitution.
p – positions is greater than that at the
9.6 Carcinogenicity and Toxicity
m-position. Hence, they are also o – and p –
directing groups. Resonance structures of Benzene and polynuclear hydrocarbons
chlorobenzene are given below: containing more than two benzene rings
fused together are toxic and said to
possess cancer producing (carcinogenic)
property. Such polynuclear hydrocarbons
are formed on incomplete combustion of
organic materials like tobacco, coal and
petroleum. They enter into human body
and undergo various biochemical reactions
and finally damage DNA and cause cancer.
Some of the carcinogenic hydrocarbons are
given below (see box).

Meta directing group: The groups which

direct the incoming group to meta position are
called meta directing groups. Some examples
of meta directing groups are –NO2, –CN, –CHO,
–COR, –COOH, –COOR, –SO3H, etc.
Let us take the example of nitro group.
Nitro group reduces the electron density in
the benzene ring due to its strong–I effect.
Nitrobenzene is a resonance hybrid of the
following structures.

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 326 chemistry

SUMMARY

Hydrocarbons are the compounds of carbon and hydrogen only. Hydrocarbons are mainly
obtained from coal and petroleum, which are the major sources of energy. Petrochemicals
are the prominent starting materials used for the manufacture of a large number of
commercially important products. LPG (liquefied petroleum gas) and CNG (compressed
natural gas), the main sources of energy for domestic fuels and the automobile industry, are
obtained from petroleum. Hydrocarbons are classified as open chain saturated (alkanes)
and unsaturated (alkenes and alkynes), cyclic (alicyclic) and aromatic, according to their
structure.
The important reactions of alkanes are free radical substitution, combustion, oxidation
and aromatization. Alkenes and alkynes undergo addition reactions, which are mainly
electrophilic additions. Aromatic hydrocarbons, despite having unsaturation, undergo
mainly electrophilic substitution reactions. These undergo addition reactions only under
special conditions.
Alkanes show conformational isomerism due to free rotation along the C–C sigma
bonds. Out of staggered and the eclipsed conformations of ethane, staggered conformation
is more stable as hydrogen atoms are farthest apart. Alkenes exhibit geometrical
(cis-trans) isomerism due to restricted rotation around the carbon–carbon double bond.
Benzene and benzenoid compounds show aromatic character. Aromaticity, the
property of being aromatic is possessed by compounds having specific electronic structure
characterised by Hückel (4n+2)π electron rule. The nature of groups or substituents attached
to benzene ring is responsible for activation or deactivation of the benzene ring towards
further electrophilic substitution and also for orientation of the incoming group. Some of
the polynuclear hydrocarbons having fused benzene ring system have carcinogenic property.

EXERCISES

9.1 How do you account for the formation of ethane during chlorination of methane ?
9.2 Write IUPAC names of the following compounds :
(a) CH3CH=C(CH3)2 (b) CH2=CH-C≡C-CH3

(c) (d) –CH2–CH2–CH=CH2

(f) CH3(CH2)4 CH (CH2)3 CH3

(e) CH2 –CH (CH3)2

(g) CH3 – CH = CH – CH2 – CH = CH – CH – CH2 – CH = CH2
|
C2H5
9.3 For the following compounds, write structural formulas and IUPAC names for all
possible isomers having the number of double or triple bond as indicated :
(a) C4H8 (one double bond) (b) C5H8 (one triple bond)
9.4 Write IUPAC names of the products obtained by the ozonolysis of the following
compounds :
(i) Pent-2-ene (ii) 3,4-Dimethylhept-3-ene
(iii) 2-Ethylbut-1-ene (iv) 1-Phenylbut-1-ene

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 Hydrocarbons 327

9.5 An alkene ‘A’ on ozonolysis gives a mixture of ethanal and pentan-3-one.

Write structure and IUPAC name of ‘A’.
9.6 An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π
bond. ‘A’ on ozonolysis gives two moles of an aldehyde of molar mass 44
u. Write IUPAC name of ‘A’.
9.7 Propanal and pentan-3-one are the ozonolysis products of an alkene? What
is the structural formula of the alkene?
9.8 Write chemical equations for combustion reaction of the following
hydrocarbons:
(i) Butane (ii) Pentene
(iii) Hexyne (iv) Toluene
9.9 Draw the cis and trans structures of hex-2-ene. Which isomer will have
higher b.p. and why?
9.10 Why is benzene extra ordinarily stable though it contains three double
bonds?
9.11 What are the necessary conditions for any system to be aromatic?
9.12 Explain why the following systems are not aromatic?

(i) (ii) (iii)

9.13 How will you convert benzene into
(i) p-nitrobromobenzene (ii) m- nitrochlorobenzene
(iii) p - nitrotoluene (iv) acetophenone?
9.14 In the alkane H3C – CH2 – C(CH3)2 – CH2 – CH(CH3)2, identify 1°,2°,3° carbon
atoms and give the number of H atoms bonded to each one of these.
9.15 What effect does branching of an alkane chain has on its boiling point?
9.16 Addition of HBr to propene yields 2-bromopropane, while in the presence
of benzoyl peroxide, the same reaction yields 1-bromopropane. Explain
and give mechanism.
9.17 Write down the products of ozonolysis of 1,2-dimethylbenzene (o-xylene).
How does the result support Kekulé structure for benzene?
9.18 Arrange benzene, n-hexane and ethyne in decreasing order of acidic
behaviour. Also give reason for this behaviour.
9.19 Why does benzene undergo electrophilic substitution reactions easily and
nucleophilic substitutions with difficulty?
9.20 How would you convert the following compounds into benzene?
(i) Ethyne (ii) Ethene (iii) Hexane
9.21 Write structures of all the alkenes which on hydrogenation give
2-methylbutane.
9.22 Arrange the following set of compounds in order of their decreasing relative
+
reactivity with an electrophile, E
(a) Chlorobenzene, 2,4-dinitrochlorobenzene, p-nitrochlorobenzene
(b) Toluene, p-H3C – C6H4 – NO2, p-O2N – C6H4 – NO2.
9.23 Out of benzene, m–dinitrobenzene and toluene which will undergo nitration
most easily and why?
9.24 Suggest the name of a Lewis acid other than anhydrous aluminium chloride
which can be used during ethylation of benzene.
9.25 Why is Wurtz reaction not preferred for the preparation of alkanes
containing odd number of carbon atoms? Illustrate your answer by taking
one example.

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