CHEMISTRY

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CHAPTER 1: SOME BASIC CONCEPTS OF CHEMISTRY

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 SOME BASIC CONCEPYS OF CHEMISTRY
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SOME BASIC CONCEPTS OF CHEMISTRY

Introduction:

Chemistry is the science of molecules and their transformations which deals with the study of
matter, its composition, the changes that matter undergoes and the relation between changes in
composition and changes in energy. Chemistry plays an important role in meeting human needs
for food, health care products.

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Branches of Chemistry:

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• Organic Chemistry- This branch deals with study of carbon compounds especially hydrocarbons
and their derivatives.

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• Inorganic Chemistry- This branch deals with the study of compounds of all other elements
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except carbon. It largely concerns itself with the study of minerals found in the Earth's crust.
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• Physical Chemistry- The explanation of fundamental principles governing various chemical
phenomena is the main concern of this branch. It is basically concerned with laws and theories of
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the different branches of chemistry.

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• Industrial Chemistry- The chemistry involved in industrial processes is studied under this branch.
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Analytical Chemistry-This branch deals with the qualitative and quantitative analysis of various
substances.
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• Biochemistry- This branch deals with the chemical changes going on in the bodies of living
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organisms; plants and animals.

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• Nuclear Chemistry- Nuclear reactions, such as nuclear fission, nuclear fusion, transmutation
processes etc. are studied under this branch.

Importance of Chemistry:

Chemistry plays a central role in science and is often intertwined with other branches of science.
Principles of chemistry are applicable in diverse areas, such as weather patterns, functioning of
brain and operation of a computer, production in chemical industries, manufacturing fertilisers,
alkalis, acids, salts, dyes, polymers, drugs, soaps, detergents, metals, alloys, etc., including new
material.

Chemistry contributes in a big way to the national economy. It also plays an important role in

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meeting human needs for food, healthcare products and other material aimed at improving the
quality of life.

Matter
Matter is any thing that occupies space, has mass, offer resistance and can be perceived of
directly by our senses. For example, book, pen, pencil, water, air, all living beings, etc.

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(1) Physical classification

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(a) Solid
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(b) Liquid
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(c) Gases

Solid Liquid Gases

They do not have fixed

(1) They have fixed They do not have fixed
shape but have fixed
shape and volume shape and volume
volume

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(2) They cannot be They cannot be They can be compressed

compressed compressed easily

(3) They have high They have moderate

They have low density
density density

(4) They do not flow They flow easily They flow easily

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(5) They do not fill They do not fill their

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They fill their container
their container container

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(6) The forces of hs
The forces of attraction The forces of attraction

attraction are strong are less strong than solids are weak.
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(7) Kinetic energy is Kinetic energy is more Kinetic energy is

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least than solids maximum.

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(8) Particles are Particles are not close as Particles are much farther
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closely packed in solids apart from one another.

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(9) For Example :

For Ex: Water, petrol, cold For Ex: Oxygen, nitrogen,
Chair, table, chalk,
drinks helium
book

Vapours represent a gaseous state of a substance which is liquid at room temperature.

A substance which is in gaseous state at room temperature is called a gas.

For Ex: Ammonia is a gas but on heating water forms vapours.

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(2) Chemical classification

All kinds of matter are classified into two types:

(a) Homogeneous

(b) Heterogeneous

Material is said to be homogeneous if it has uniform composition and identical properties

throughout Or a material is said to be homogeneous if it consist of only one phase.

A material is said to be heterogeneous if it consists of a number of phases. The different

phases are separated from each other by distinct boundaries.

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Element
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Element is the purest form of matter. It is made up of only one type of atoms, ex.- carbon, iron,
copper, oxygen etc.

Compound
Compound is the substance which is made up of two or more elements combined together in a
fixed ratio by their weight e.g., carbon dioxide.

Mixture
Mixture is the substance which is made up of two or more substances in any ratio. e.g.,
Sugar + Water, Sodium Chloride + Water, Sand + Water

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On the basis of composition, mixtures are of following type:

➢ Homogeneous mixture: The mixture which has uniform composition through out e.g., sugar
solution.

➢ Heterogeneous mixture: The mixtures which do not have uniform composition through out. e.g.
sand in water.

Atom
Atom is the smallest particle which may or may not exist free but takes part in chemical reaction.
Atom word means not to be cut. Ex- H, Na, O etc.

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International System of Units (S.I.)

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The international system of units (in French Le Systeme International d' Unités - abbreviated as

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SI) was established in 1960 by the 11th general conference on weights and measures. SI system
is a modification of metric system and has seven base units pertaining to the seven fundamental

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scientific quantities. hs
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Prefixes in SI system

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Definition of SI Base Units hs
• Metre: The metre is the length of the path travelled by light in vacuum during a time interval of
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1/(299792458) of a second.
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• Kilogram: The kilogram is the unit of mass; it is equal to the mass of the international prototype
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of the kilogram.
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• Second: The second is the duration of 9192631770 periods of the radiation corresponding to the
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transition between the two hyperfine levels of the ground state of the caesium-133 atom.
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• Ampere: The ampere is that constant current which, if maintained in two straight parallel
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conductors of infinite length, of negligible circular cross-section, and placed 1 metre apart in
vacuum, would produce between these conductors a force equal to 2 × 10-7 newton per metre of
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length.

• Kelvin: The kelvin, unit of thermodynamic temperature, is the fraction 1/273.16 of the
thermodynamic temperature of the triple point of water.

• Mole: The mole is the amount of substance of a system which contains as many elementary
entities as there are atoms in 0.012 kilogram of carbon-12; its symbol is “mol”.

• Candela: The candela is the luminous intensity, in a given direction, of a source that emits
monochromatic radiation of frequency 540 × 1012 hertz and that has a radiant intensity in that
direction of 1/683 watt per steradian.

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Uncertainty in Measurement
All scientific measurements involve certain degree of error or uncertainty. Scientific notations,
significant figures and dimensional analysis help us in many ways in presenting of data and
theoretical calculations.

Scientific Notation

It is an exponential notation in which any number can be represented in the form N × 10n where
n is an exponent having positive or negative values and N can vary between 1 to 10. Thus,
232.508 can be written as 2.32508 × 102 in scientific notation.

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Precision and Accuracy

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Precision refers to the closeness of various measurements for the same quantity. However,
accuracy is the agreement of a particular value to the true value of the result. Let the true value

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of a quantity is 3.9 and its measurements taken by two boys are 3.6 and 3.8. Here 3.8 is more
accurate as it is closer to the true value. Similarly 3.85 is more precise than 3.9.

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Significant Figures
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i. The total number of digits in measuring of any physical quantity with certainty is called
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significant figures. There are certain rules for determining the number of significant figures.
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ii. All digits are significant except zero in the beginning of a number. For example, in 285 cm, there
are three significant figures.
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iii. Zeros to the left of the first non-zero digit are not significant if such zeros follow the decimal
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point. For example, 0.03 has one significant figure.

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iv. Zeros to the right of the decimal point are significant. For example, 0.200 g has three significant
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figures.
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v. Zeros between two non-zero digits are significant. Thus, 2.005 has four significant figures.

vi. Counting the numbers of object, for example, 2 balls or 20 eggs, have infinite significant figures
as these are exact numbers and can be represented by writing infinite number of zeroes after
placing a decimal i.e., 2 = 2.000000 or 20 = 20.000000.

Notes: In additions or subtractions, the final result should be reported to the same number of
decimal places as that of the term with the least number of decimal places.

Laws of Chemical Combination

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All chemical reactions take place according to certain laws. These laws are known as laws of
chemical combination.

i. Law of conservation of mass: This law was put forth by Antoine Lavoisier in 1789. According to
this, "It states that the total mass of reactants is equal to the total mass of the products".

ii. Law of constant composition: This law was given by, a French chemist, Joseph Proust. This law
states that a chemical compound is always found to be made of same elements combined
together in fixed proportion by weight. CO2 can be prepared by number of methods but always
12g carbon react with 32g of oxygen.

iii. Law of multiple proportions: This law was proposed by Dalton in 1803. According to this law,

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When two elements combine to form two or more chemical compounds, then weight of one of
the element which combines with a fixed weight of the other, bears a simple whole number ratio

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to one another. This is called the law of multiple proportions.
For example, The ratio of masses of oxygen in CO and CO2 for fixed mass of carbon (12) is 16 : 32

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= 1 : 2.

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iv. Law of reciprocal proportions: It states that the ratio of weights of two elements A and B, which
combine separately with the fixed weight of a third element C is either same or some simple
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whole number of the ratio of weights in which A and B combine directly with each other.
For example, ratio of masses of carbon and sulphur which combine with the fixed mass (32
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parts) of oxygen is 12 : 32 or 3 : 8.
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v. Gay Lussac’s Law of Gaseous Volumes: This law was given by Gay Lussac in 1808. He observed
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that when gases combine or are produced in a chemical reaction they do so in a simple ratio by
volume, provided all gases are at the same temperature and pressure.
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For example, One volume of hydrogen and one volume of chlorine always combine to form two
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volumes of HCl gas.

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vi. Avogadro’s Law: In 1811, Avogadro proposed that equal volumes of all gases at the same
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temperature and pressure should contain equal number of molecules.

Dalton's Atomic Theory

John Dalton in 1808 published “A New System of Chemical Philosophy” in which he proposed
atomic theory of matter. The main points of Dalton’s atomic theory are as follows:

i. Matter is made up of extremely small, indivisible particles called atoms.

ii. Atoms of a given element are identical in all respect, i.e., they possess same size, shape, mass,
chemical properties etc.

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iii. Atoms of different elements are different in all respects, i.e., they possess different sizes, shapes,
masses, chemical properties etc.

iv. Atoms of different elements may combine with each other in a fixed, simple, whole number ratio
to form compounds.

v. Atoms can neither be created nor destroyed in a chemical reaction. Dalton’s theory could explain
the laws of chemical combination.

Atomic Mass and Molecular Mass

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a) Atomic Mass: Atomic mass can be defined as a mass of a single atom which is measured in

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atomic mass unit (amu) or unified mass (u) where,

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1 a.m.u. = 𝐭𝐡 of the mass of one C-12 atom
𝟏𝟐

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b) Molecular Mass: Molecular mass is the sum of atomic masses of the elements present in a

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molecule. It is obtained by multiplying the atomic mass of each element by the number of its
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atoms and adding them together. Molecular mass expressed in grams is known as gram
molecular mass.
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Molecular mass of methane,
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(CH4) = (12.011 u) + 4 (1.008 u) = 16.043 u

The Mole
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One mole is the amount of substance that contains as many as entities as number of atoms in
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exactly 12.00g of C-12.

Number of carbon atoms in 12 g of C-12 = 6.022 × 1023
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Chemical Formulae
Symbolic representation of compound is called chemical formula. It is of following types:

a) Empirical Formula: An empirical formula represents the simplest whole number ratio of various
atoms present in a compound.

b) Molecular Formula: The molecular formula shows the exact number of different types of atoms
present in a molecule of a compound.

Relationship between Empirical and Molecular Formula

Molecular formula = (Empirical formula) × n

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Measurement of Concentration
The concentration of a solution reflects the relative proportion of solute and solvent present in
the solution. The various concentration terms are,

1. Weight percent (% w/W) = (Weight of solute / Weight of solution) × 100.

2. Volume percent (% V/V) = (Volume of solute / Volume of solution) × 100.

3. Molality (m) – It is defined as number of moles of solute present in 1kg of solvent.

m = {Number of moles of solute/Mass of solvent (in kg)} × 100.

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4. Molarity (M) – It is defined as number of moles of solute present in 1 L of solution.

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M = {Number of moles of solute/Volume of solution (in litre)} × 100

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5. Mole fraction : Suppose, n is the moles of solute and N is the moles of solvent, then,

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(i). Mole fraction of solute (Xsolute) = hs
n+N

N
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(ii). Mole fraction of solvent (Xsolvent) =
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Xsolute + Xsolvent = 1
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6. Normality: It is defined as gram equivalent of solute dissolved in one litre solution.

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Gram equivalent of solute

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N =
Volume of solution (litre) × 100
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Limiting Reagent
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Limiting reagent is the reactant which is completely consumed in a reaction. To estimate the
amount of product, limiting reagent should be known.

N2(1 mole) + 3H2(3 mole) ⟶ 2NH3(2 mole)

It means 1 mole of N2 react with 3 mole of H2 to produce 2 mole of NH3.

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Quantities

Physical Quantities

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Physical Properties

Physical Properties are those which can be measured or observed without changing the identity
or composition of the substance.

For example : Mass, volume, melting point, boiling point.

Chemical properties

Chemical properties are those in which a chemical change in the substance occurs.

The measurement of any physical quantity consists of two parts:

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(a) The number

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(b) The unit

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For example: If an object weighs 4.5 kg it involves two parts:

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4.5 is the number and kg is the unit.
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A unit is defined as the standard of reference chosen to measure any physical quantity.
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French Academy of science in 1791 introduced a new system of measurement called metric
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system in which the different units of a physical quantity are related to each others as multiples
of powers of 10.
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For example: The improve System of units has been accepted internationally and is called
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International.
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System of units or in short SI units (Systeme Internationale in French).

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Seven base units

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The seven basic physical quantities on which the international System of units is based, their
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symbols, the name of their units and the symbols of these units are given as:

Seven basic units

Measurement of Temperature

There are 3 scales of temperature:

(1) Degree Celsius

(2) Degree Fahrenheit

(3) Kelvin

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The SI unit of Temperature is Kelvin

Relation between Degree kelvin and degree Celsius

Fahrenheit and Celsius relation

Relation between degree celsius and Degree Fahrenheit

Fahrenheit and Celsius relation

Measurement of Volume

The SI unit of volume is m³

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1 L =1000 mL =1000 cm³

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1 L = 1 dm³

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1 m³ = 100 (cm)³ = 10³ L

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Measurement of Mass hs
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Mass is the quantity of matter contained in the sample and for the given sample it is constant
and it does not depend upon the place.
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weight is the force with with which the body is attracted towards the earth. It depends upon the
acceleration due to gravity which varies from place to place. The mass of a substance can be
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determined very accurately in the laboratory by using analytical balance or electrical balance.
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S.I. unit of mass is kilogram

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1 Kg =1000 g
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Units of Length
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The S. I. unit of length is metre. It is also expressed in angstroms or nanometres or picometres.

Commonly used physical quantities and their derived units

Physical quantities and their derived units

Avogadro’s hypothesis
Berzelius a Swedish chemist, gave a hypothesis called Berzelius hypothesis which states that :

Equal volume of all gases under similar conditions of temperature and pressure contain equal
number of atoms.

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For Example : Hydrogen + Chlorine —————-> 2 Hydrogen chloride gas

1 vol 1 vol 2 vol

n atoms n atoms 2n molecule

On dividing throughout by 2n

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This implies that one compound atom of hydrogen chloride is made up of ½ atom of hydrogen
and ½ atom of chlorine. This is in direct conflict with Dalton’s atomic theory which states that

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atoms are the ultimate particles of elements and are indivisible. This hypothesis was therefore

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rejected.

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Avogadro’s hypothesis

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It states that equal volume of all gases under similar condition of temperature and pressure

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contain equal number of molecules .

Applications of Avogadro’s law

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1) In the calculation of atomicity of Elementary gases :
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Atomicity of an elementary substance is defined as the number of atoms of the element present
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in 1 molecule of the substance.

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For example : Atomicity of oxygen is 2 while that of ozone is 3.

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Hydrogen + oxygen ——
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2n molecules n molecules 2n molecules

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On dividing throughout by 2n

1 molecule ½ molecule 1 molecule

Thus one molecule of water contains ½ molecule of oxygen. But 1 molecule of water contains 1
atom of oxygen.

Hence ½ molecule = 1 molecule of oxygen

1 molecule of oxygen= 2 atoms of oxygen = 1 atom of oxygen= 2

2) To find the relationship between molecular mass and vapour density of a gas

Molecular mass = 2 × vapour density

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3) To find the relationship between mass and volume of a gas 22.4 litres of any gas at STP weigh
equal to the molecular mass of the gas expressed in grams. This is called gram molecular volume
law.

Atomic and Molecular mass

As an atom is so small a particle that it cannot be seen or isolated ,therefore it is impossible to
determine the actual mass of a single atom by weighing it.

The problem was finally solved by Avogadro’s hypothesis. If equal volumes of two different gases
are taken under similar conditions of temperature and pressure and then weighted, the ratio of
their masses will be equal to the ratio of their single molecules. Thus, though the actual masses

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of the atoms could not be determined but their relative masses could be determined. If the
atomic mass of the hydrogen is taken is 1 ,the relative atomic mass of oxygen is 16 .

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Initially, the atomic masses of all the elements were obtained by comparing with the mass of

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hydrogen taken as 1 but by doing so, the atomic masses of most of the elements came out to be

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fractional.
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Therefore carbon is taken reference for the determination of atomic masses.
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Atomic mass of an element is the number of times an atom of that element is heavier than an
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atom of carbon taken as 12.

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One atomic mass unit is equal to one twelfth of the mass of an atom of carbon 12 isotope.
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The atomic mass of an element is the average relative mass of its atoms as compared with an
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atom of carbon 12 taken as 12.

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Fractional abundance of an isotope is the fraction of the total number of atoms that is comprised
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of that particular isotope.

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Fractional abundance

Gram Atomic mass

The atomic mass of an element expressed in grams is called gram atomic mass.

For Ex: Atomic mass of oxygen is 16 amu.

Gram atomic mass of oxygen = 16 g.

Molecular mass

The molecular mass of a substance is the number of times the molecule of the substance is

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heavier than one twelfth the mass of an atom of carbon -12.

or

The molecular mass is equal to sum of its atomic masses of all the atoms present in one
molecule of substance.

For Example : Mass of H= 1 u

Atomic mass of O =16 u

Molecular mass of water =2 × atomic mass of H+1 × atomic mass of O

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=2 × 1 + 16 × 1

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= 18 u

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Gram molecular mass

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The molecular mass of a substance expressed in grams is called gram molecular mass.
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For Example : Molecular mass of oxygen = 32u
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Gram molecular mass of oxygen = 32 g
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Mole Concept
1 Avogadro’s number or Avogadro’s constant (NA)
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2 Mole
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3 Importance of Avogadro’s number and Mole Concept

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Avogadro’s number or Avogadro’s constant (NA)

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One gram atom of any element contains the same number of atoms and one gram molecule of
any substance contains the same number of molecules.

The value was found to be 6.022137 × 1023

The value generally used is 6.022 × 1023 .

This is called Avogadro’s number or Avogadro’s constant (NA)

Avogadro’s number may be defined as the number of atoms present in one gram atom of the
element or the number of molecules present in one gram molecule of the substance.

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A mole is a chemist unit of counting particles such as atom, molecules, ions, electrons, protons
which represent a value of 6.022 × 1023

A mole of hydrogen atom means 6.022 × 1023 atoms of hydrogen whereas a mole of hydrogen
molecule means 6.022 × 1023 molecules of hydrogen or 2 × 6.022 × 1023 atoms of hydrogen .

A mole of oxygen molecule means 6.022 × 1023 molecules of oxygen or 2 × 6.022 × 1023 atoms of
oxygen.

A mole is defined as that amount of substance which has mass equal to gram atomic mass if the
substance is atomic or gram molecular mass if the substance is molecular.

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1 mole of carbon atoms =12 grams

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1 mole of sodium atoms = 23 grams

1 mole of Oxygen atom = 16 grams

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1 mole of Oxygen molecule = 32 grams

1 mole of water molecule = 18 grams

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1 mole of carbon dioxide molecule = 44 grams
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Mole
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A mole is defined as that amount of substance which contains Avogadro’s number of atoms if
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the substance is atomic or Avogadro’s number of molecules if the substance is molecular.

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1 mole of carbon atoms = 6.022 ×1023 atoms of carbon.

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1 mole of sodium atom = 6.022 ×1023 atoms of sodium

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1 mole of Oxygen atom = 6.022 ×1023 atoms of oxygen

1 mole of Oxygen molecule = 6.022 ×1023 molecules of oxygen

1 mole of water = 6.022 ×1023 molecules of water

In case of gases, a mole is defined as that amount of the gas which has a volume of 22.4 litres at
STP.

1 mole of Oxygen gas = 22.4 litres of oxygen at STP

one mole of carbon dioxide gas = 22.4 litres of carbon dioxide at STP

A mole of an ionic compound is defined as that amount of the substance which has mass equal

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to gram formula mass or which contains Avogadro’s number of formula unit.

1 mole of NaCl = 58.5 grams of NaCl

1 mole of NaCl = 6.022 ×1023 formula units of NaCl = 6.022 ×1023 Na+ ion and 6.022 ×1023

Cl– ion.

Importance of Avogadro’s number and Mole Concept

In the calculation of actual mass of a single atom of an element or a single molecule of a

substance.

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In the calculation of the number of atoms or molecules in a given mass of the element of the
compound.

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In the calculation of the number of molecules present in a given volume of the gas under given

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conditions.

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In the calculation of the size of the individual atoms and molecules assuming them to the
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spherical.
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In the calculation of actual masses of 1 amu or 1 u.
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1 amu = 1.6606 × 10-24 g

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1 amu = 1.6606 × 10-27 kg

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Empirical and Molecular Formula

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Calculation of percentage composition

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The percentage of any element or constituent in a compound is the number of parts by mass of
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that element or constituent present in 100 parts by mass of the compound.

Step 1 : Calculate the molecular mass of the compound from its formula by adding the atomic
masses of the element present.

Step 2 : Calculate the percentage of elements or the constituents by applying the relation:

Percentage composition

Question : Calculate the percentage of Carbon, Hydrogen and oxygen in Ethanol?

24.022 𝑔
Answer : mass % C = × 100 % = 52.144 %
46.069 𝑔

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6.048 𝑔
Mass % H = × 100 % = 13.13%
46.069 𝑔

15.999 𝑔
Mass % O = × 100 % = 34.72 %
46.069 𝑔

Empirical and Molecular Formula

The empirical formula of a compound is the chemical formula which expresses the simplest
whole number ratio of the atoms of the various elements present in one molecule of the
compound.

For Ex: The empirical formula of benzene is CH, hydrogen peroxide is HO, Glucose is CH2O.

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The empirical formula represents only the atomic ratio of the various elements present in its

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molecule.

The molecular Formula of a compound is the chemical formula which represents the true

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formula of its molecules. It expresses the actual number of atoms of various elements present in

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one molecule of the compound.
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The molecular formula of benzene is C6H6 , hydrogen peroxide is H2O2 , Glucose is C6H6.
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Molecular Formula = n × Empirical formula
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where n is any integer such as 1, 2, 3 ,4 etc.

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The value of n can be obtained from the relation:

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calculation of n
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Molecular mass = 2 × Vapour Density

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Calculation of Empirical Formula

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Step 1 : Convert the mass percentage into grams.

Step 2 : Calculate the number of moles.

number of moles

Step 3 : Calculate the simplest molar ratio: Divide the moles obtained in step 1 by the smallest
quotient or the least value from amongst the values obtained for each element.

Step 4 : Calculate the simplest whole number ratio.

Step 5 : Write the empirical formula.

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Empirical Formula

The empirical Formula is C2H4O.

Calculation of molecular Formula

The molecular formula of a compound can de deduced from:

1) Empirical Formula

2) Molecular mass

Step 1 Calculation of the empirical formula from the percentage composition.

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Step 2 Calculation of empirical formula mass by adding the atomic mass of all the atoms present

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in the empirical formula.

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Step 3 Determination of the molecular mass of the compound from the given data.

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Step 4 Determination of the value of n.
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Step 5 Determination of the molecular formula
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Question A compound contains 4.07 % hydrogen, 24.27 % carbon and 71.65 % chlorine.Its molar
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mass is 98.96 g.What are its empirical and molecular formula.

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Answer
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Simplest
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Percentage Moles of Simplest

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Element Symbol Atomic mass Whole no.

Of element element Molar ratio
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Molar ratio

Carbon C 24.27 12 2.02 1 1

Hydrogen H 4.07 1 4.07 2 2

Chlorine Cl 71.65 35.5 2.02 1 1

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 SOME BASIC CONCEPYS OF CHEMISTRY
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The empirical formula of the compound is CH2Cl

Empirical mass of CH2Cl = 12 + 2 ×1 +35.5 = 49.5

n=2

Molecular formula = n × E. F.

= 2 × CH2Cl

= C2H4Cl2

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Balancing Of A Chemical Equation

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Balancing of a chemical equation means making the number of atoms of each element equal on

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both sides of the equation.

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The methods of balancing equation are: hs
1) Hit and Trial Method:
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The simplest method to balance a chemical equation is by hit and trial method.
lp
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Step 1 : Write down the correct formula of the reactants and products with plus sign in between
with an arrow pointing from reactants to Products. This is called skeletal equation.
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Step 2: Select the biggest formula from the Skeleton equation and equalise the number of atoms
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of each of its constituent elements on both sides of the chemical equation by suitable
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multiplication .
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Step 3: When an elementary gas appear as a reactant or a product ,the equation is balanced
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more easily by keeping the elementary gas in the atomic state. The balanced atomic equation is
then made molecular by multiplying the whole equation by 2.

Question : Magnetic oxide when heated with hydrogen is reduced to iron and water is also
produced. Write balanced equation for the reaction?

Answer : Magnetic oxide + Hydrogen ———-> Iron + Water

Fe3O4 + H2 ——–> Fe + H2O

To equalise the number of atoms of Fe on both sides, multiply Fe by 3 , we have

Fe3O4 + H2 ——–> 3Fe + H2O

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

The above equation has 4 atoms of O on L.H.S. and 1 atoms of O on R.H.S.

To equalise, multiply water by 4.

Fe3O4 + H2 ——–> 3Fe + 4H2O

The above equation has 8 H atoms on R.H.S. and 2 H atoms on L.H.S.

To equalise ,multiply H2 on L.H.S. by 4

Fe3O4 + 4H2 ——–> 3Fe + 4H2O

This a balanced chemical equation

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2) Partial Equation method

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Step 1 The chemical reaction represented by the equation is supposed to proceed in two or

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more steps.

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Step 2 The Skeleton equation representing each step are written and then balanced by hit and
hs
trial method. These equations are known as partial equations.
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Step 3 If necessary the partial equation are multiplied by suitable integers so as to cancel those
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intermediate products which do not occur in the final reaction .

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Step 4 The partial equations are added up to get the final balanced equation.
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Question : The skeleton equation to represent the action of chlorine on a hot solution of sodium
hydroxide is
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NaOH + Cl2 ————> NaCl + NaClO3 + H20

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Balance this equation by the method of partial equations

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Answer : Cl2 + H2O ———-> H2O + HCl

NaOH + HCl ————> NaCl + H2O

NaOH + HClO ———–> NaClO + H2O

3 NaClO ———–> 2 NaCl + NaClO3

3 Cl2 + 6 NaOH ————> 5 NaCl + NaClO3 + 3 H2O

Summary-

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

1. Matter: Anything that occupies space and has mass.

2. Element: A pure substance which can neither be decomposed into nor built from simpler
substances by any physical or chemical method. It contains only one kind of atoms.

3. Compound: A pure substance which can be decomposed into simpler substances by some
suitable chemical method. It contains only one kind of molecules.

4. Mixture: A substance obtained by simple mixing of two or more pure substances.

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5. Law of Conservation of Mass: During any physical or chemical change total mass of the products

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formed is equal to the total mass of the reactants consumed.

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6. Law of Constant Composition: A chemical compound always contains same elements combined

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together in same proportion of mass.

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hs
7. Law of Multiple Proportions: When two elements combine with each other to form two or more
than two compounds then the masses of one of the elements that combine with the fixed mass
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of the other, bear a simple whole number ratio to one another.
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8. Gay Lussac's law: When gases react with each other they do so in volumes which bear a simple
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whole number ratio to one another and to the volumes of products, if there are also gases,
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provided all volumes are measured under similar conditions of temperature and pressure.
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9. Avogadro's Law: Equal volume of all gases under similar conditions contain equal number of
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molecules.
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10. Atom: The smallest particle of an element that takes part in chemical reactions.
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11. Molecule: The smallest particle of a substance that has independent existence.

12. Atomicity: The number of atoms in a molecule of the elementary substance.

13. Unified Mass (u): One-twelfth of the actual mass of an atom of carbon (C-12). It is equal to 1.66
× 10–27 kg.

14. Atomic Mass: The average relative mass of an atom of the element as compared with mass of a
carbon atom (C-12) taken as 12 u.

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

15. Molecular Mass: The average relative mass of a molecule of the substance as compared with
mass of an atom of carbon (C-12) taken as 12 u.

16. Gram Atomic Mass: The mass of 1 mole of atoms (6 × 1023) in g is called gram atomic mass.

17. Gram Molecular Mass: The mass of 1 gram molecule of compound expressed in grams.

18. Avogadro's Number (NA): 6.022 × 1023.

19. Mole: 6.022 × 1023 specified particles.

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20. Molar Mass: Mass of one mole particles of the substance.

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21. Gram Molecular Volume (G.M.V.): Volume occupied by one mole molecules of the gaseous

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substance. Its value is equal to 22.4 L and S.T.P.

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hs
22. Empirical Formula: The formula which gives the simplest whole number ratio of atoms of
different elements present in the molecule of the compound. Molecular formula is whole
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number multiple of empirical formula.
lp
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23. Molarity (M): Number of moles of solute per litre of solution. Expressed as moles per litre or
moles per dm3 or Molar (M).
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24. Molarity changes with change in temperature because volume of the solution changes with
change in temperature.
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25. K = °C + 273.15
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9
26. °F = (°C) + 32
5

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

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hs
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 SOME BASIC CONCEPYS OF CHEMISTRY
01

Important Questions
Multiple Choice questions-
Question 1. Formula of Ferric Sulphate is:
(a) FeSo4
(b) Fe (So4)3
(c) Fe2 (So4)3
(d) Fe2So4
Question 2. Approximate atomic weight of an element is 26.89. If its equivalent weight is 8.9, the

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exact atomic weight of element would be

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(a) 26.89

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(b) 8.9

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(c) 17.8

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(d) 26.7 hs
Question 3. The total number of atoms represented by the compound CuSO4. 5H2O is
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(a) 27
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(b) 21
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(c) 5
(d) 8
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Question 4. An atom is 10 times heavier than 1/12th of mass of a carbon atom (C – 12). The mass of
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the atom in a.m.u. is

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(a) 10
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(b) 120
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(c) 1.2
(d) 12
Question 5. 81.4 g sample of ethyl alcohol contains 0.002 g of water. The amount of pure ethyl
alcohol to the proper number of significant figures is
(a) 81.398 g
(b) 71.40 g
(c) 91.4 g
(d) 81 g
Question 6. Which of the following halogen can be purified by sublimation?

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

(a) F2
(b) Cl2
(c) Br2
(d) I2
Question 7. 1 mol of CH4 contains
(a) 6.02 × 1023 atoms of H
(b) 4 g atom of Hydrogen
(c) 1.81 × 1023 molecules of CH4

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(d) 3.0 g of carbon

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Question 8. The prefix zepto stands for

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(a) 109

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(b) 10-12

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(c) 10-15
(d) 10-21
hs
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Question 9. Which has maximum number of atoms?
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(a) 24 g of C (12)
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(b) 56 g of Fe (56)
(c) 27 gof Al (27)
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(d) 108 g of Ag (108)

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Question 10: Irrespective of the source, pure sample, of water always yields 88.89% mass of oxygen
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and 11.11% mass of hydrogen. This is explained by the law of

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(a) Conservation of Mass

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(b) Multiple Proportions

(c) Constant Composition
(d) Constant Volume
Question 11. Hemoglobin contains 0.33% of iron by weight. The molecular weight of hemoglobin is
approximately 67200. The number of iron atoms (At. wt. of Fe = 56) present in one molecule of
hemoglobin is
(a) 6
(b) 1
(c) 4

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

(d) 2
Question 12. The -ve charged particles is called:
(a) Anion
(b) Cation
(c) Radical
(d) Atom
Question 13. Which of the following contains same number of carbon atoms as are in 6.0 g of
carbon (C – 12)?

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(a) 6.0 g Ethane

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(b) 8.0 g Methane

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(c) 21.0 g Propane
(d) 28.0 g CO

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Question 14. The density of a gas is 1.78 gL-1 at STP. The weight of one mole of gas is

a
(a) 39.9 g
hs
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(b) 22.4 g
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(c) 3.56 g
(d) 29 g
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Question 15. Molarity of 0.2 N H2SO4 is

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(a) 0.2
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(b) 0.4
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(c) 0.6
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(d) 0.1
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Very Short:
1.What is chemistry?
2. How has chemistry contributed towards nation’s development?
3. Differentiate solids, liquids & gases in terms of volume & shapes.
4. Name the different methods that can be used for separation of components of a mixture.
5. Classify following as pure substances and mixtures – Air, glucose, gold, odium and milk
6. What is the difference between molecules and compounds? Give examples of each.?
7. How can we separate the components of a compound?

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

8. How are physical properties different from chemical properties?

9. What are the two different system of measurement?
10. What is the SI unit of density?

Short Questions:
1. Define Mole. What is its numerical value?
2. Define molarity. Is it affected by a change in temperature?
3. What do you mean by Precision and accuracy?

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4. Distinguish between fundamental and the derived units.

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5. Define molality and write its temperature dependence.

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6. Distinguish between an atom and a molecule.
7. Derive the SI unit of Joule (J) in terms of fundamental units.

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Long Questions: hs
1. State the law of Multiple Proportions. Explain with two examples.
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2. State the law of Constant Composition. Illustrate with two examples.
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3. Define empirical formula and molecular formula. How will you establish a relationship between the
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two? Give examples.

4. In the commercial manufacture of nitric acid, how many moles of NO2 produce 7.33 mol HN03 in
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the reaction
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3 NO2(g) + H2O(1) → 2HNO3(aq) + NO(g)

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5. A sample of NaNO3 weighing 0.83 g is placed in a 50,0 mL volumetric flask. The flask is then filled
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with water upon the etched mark. What is the molarity of the solution?
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Assertion Reason Questions:

1. In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is
given. Choose the correct option out of the choices given below each question.

Assertion (A) : The empirical mass of ethene is half of its molecular mass.
Reason (R) : The empirical formula represents the simplest whole-number
ratio of various atoms present in a compound.
(i) Both A and R are true and R is the correct explanation of A.
(ii) A is true but R is false.

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

(iii) A is false but R is true.

(iv) Both A and R are false.

2. In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is
given. Choose the correct option out of the choices given below each question.

Assertion (A) : One atomic mass unit is defined as one twelfth of the mass of
one carbon-12 atom.
Reason (R) : Carbon-12 isotope is the most abundunt isotope of carbon
and has been chosen as standard.

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(i) Both A and R are true and R is the correct explanation of A.

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(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.

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(iv) Both A and R are false.

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Case Study Based Question: hs
1. Chemistry is the science of molecules and their transformations. It is the science not so much of the
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one hundred elements but of the infinite variety of molecules that may be built from them.
lp

Chemistry plays a central role in science and is often intertwined with other branches ofscience.to
understand the basic concepts of chemistry, which begin with the concept of matter. Let us start
ita

with the nature of matter. matter can exist in three physical states viz. solid, liquid and gas.
Particles are held very close to each other in solids in an orderly fashion and there is not much
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freedom of movement. In liquids, the particles are close to each other but they can move around.
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However, in gases, the particles are far apart as compared to those present in solid or liquid states
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and their movement is easy and fast. different states of matter exhibit the following characteristics:
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I. Solids have definite volume and definite shape.

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II. Liquids have definite volume but do not have definite shape. They take the shape of the container
in which they are placed.
II. Gases have neither definite volume nor definite shape. They completely occupy the space in the
container in which they are placed.
Matter can be classified as mixture or pure substance. A mixture may be homogeneous or
heterogeneous. Pure substances can further be classified into elements and compounds. Particles
of an element consist of only one type of atoms. These particles may exist as atoms or molecules.
When two or more atoms of different elements combine together in a definite ratio, the molecule
of a compound is obtained.

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

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, reactivity with acids and bases, etc.
Physical properties can be measured or observed without changing the identity or the composition
of the substance. The measurement or observation of chemical properties requires a chemical
change to occur. Measurement of physical properties does not require occurrence of a chemical
change.
(1) Which of the following state of matter have definite volume but do not have definite shape ?
(a) Solid

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(b) Liquid

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(c) Gas

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(d) Plasma

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(2) Particles are held very close to each other in … in an orderly fashion and there is not much

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freedom of movement.
(a) Liquid
hs
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(b) Gas
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(c) Solid
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(d) Plasma
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(3) Particles of …. consist of only one type of atom.

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(a) Compound
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(b) Mixture
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(c) Element
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(d) All the above

(4) Water molecule comprises …hydrogen atoms and … oxygen atom.
(a) One , two
(b) Three , one
(c) One , three
(d) Two , one
(5) Which of the following is not an example of Physical Properties of substance.?

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

(a) Odour
(b) Melting point
(c) Density
(d) Composition
2. The uncertainty in the experimental or the calculated values is indicated by mentioning the number
of significant figures. Significant figures are meaningful digits which are known with certainty plus
one which is estimated or uncertain. The uncertainty is indicated by writing the certain digits and
the last uncertain digit. there are certain rules for determining the Number of significant figures.
These are Stated below:

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• All non-zero digits are significant. For Example in 285 cm, there are three Significant figures and in

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0.25 mL, there are two significant figures.
• Zeros preceding to first non-zero digit are not significant. such zero indicates the position of

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decimal point. thus, 0.03 has one significant figure and 0.0052 has two significant figures.

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• Zeros between two non-zero digits are significant. thus, 2.005 has four Significant figures.
•
hs
Zeros at the end or right of a number are significant, provided they are on the right side of the
decimal point. For example, 0.200 g has three significant figures. But, if otherwise, the terminal
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zeros are not significant if there is no decimal point.
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Precision refers to the closeness of various measurements for the same quantity. However,
accuracy is the agreement of a particular value to the true value of the result.
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LAWS OF CHEMICALCOMBINATIONS- The combination of elements to form compounds is

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governed by the following five basic laws.

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1) Law of Conservation of Mass- This law was put forth by Antoine Lavoisier in 1789. He performed
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careful experimental studies for combustion reactions and reached to the conclusion that in all
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physical and chemical changes, there is no net change in mass during the process. Hence, he
reached to the conclusion that matter can neither be created nor destroyed. This is called ‘Law of
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Conservation of Mass’.
2) Law of Definite Proportions- This law was given by, a French chemist, Joseph Proust. He stated
that a given compound always contains exactly the same proportion of elements by weight.
3) Law of Multiple Proportions- This law was proposed by John Dalton. According to this law, if two
elements can combine to form more than one compound, the masses of one element that combine
with a fixed mass of the other element, are in the ratio of small whole numbers. For example,
hydrogen combines with oxygen to form two compounds, namely, water and hydrogen peroxide.
Hydrogen + Oxygen→ Water
2g 16g 18g

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

Hydrogen + Oxygen → Hydrogen Peroxide

2g 32g 34g
Here, the masses of oxygen (i.e., 16 g and 32 g), which combine with a fixed mass of hydrogen (2g)
bear a simple ratio, i.e., 16:32 or 1:2.
4) Gay Loussac’s Law of Gaseous Volumes- This law was given by Gay Loussac in 1808. He
observed that when gases combine or are produced in a chemical reaction they do so in a simple
ratio by volume, provided all gases are at the same temperature and pressure.
5) Avogadro’s Law- In 1811, Avogadro proposed that equal volumes of all gases at the same
temperature and pressure should contain equal number of molecules.

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In 1808, Dalton published ‘A New System of Chemical Philosophy’, in which he proposed the

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following :
(1) Matter consists of indivisible atoms.

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(2) All atoms of a given element have identical properties, including identical mass. Atoms of

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different elements differ in mass. hs
(3) Compounds are formed when atoms of different elements combine in a fixed ratio.
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(4) Chemical reactions involve reorganisation of atoms. These are neither created nor destroyed in
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a chemical reaction.
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1) ………… refers to the closeness of various measurements for the same quantity.
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a) Accuracy
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b) Reliability
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c) Precision
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d) Uncertainty
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2) Law of Conservation of mass was put forth by ………. in 1789.

a) Joseph Proust
b) Antoine Lavoisier
c) Joseph Louis
d) Gay Loussac
3) Which of the following number has two significant figures.
a) 00052

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

b) 052
c) 52
d) 0.0052
4) ……….. is the agreement of a particular value to the true value of the result.
a) Accuracy
b) Reliability
c) Precision

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d) Uncertainty

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5) Law of Multiple Proportions proposed by ..

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a) Joseph Proust

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b) Antoine Lavoisier

a
c) Joseph Louis hs
d) John Dalton
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Answer Key:
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MCQ
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1. (c) Fe2 (So4)3

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2. (a) 26.89
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3. (b) 21
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4. (a) 10

5. (a) 81.398 g

6. (d) I2

7. (c) 4 g atom of Hydrogen

8. (d) 10-21

9. (a) 24 g of C (12)

10.(c) Constant Composition

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

11.(c) 4

12.(a) Anion

13.(b) 8.0 g Methane

14.(a) 39.9 g

15.(d) 0.1

Very Short Answer:

)
1. Chemistry is the branch of science that studies the composition, properties and interaction of

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matter.

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2. chemical principles are important in diverse areas such as weather patterns, functioning of brain,
operation of a computer, chemical industries, manufacturing , fertilizers, alkalis, acids, salts, dyes,

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polymers, drugs, soaps, detergents, metals, alloys, contribute in a big way to national economy.

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3.
hs
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roperty Solids Liquids Gases
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1. Volume Definite Definite Not definite

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Not fixed,
Not fixed, take
takes the
2. Shape Fixed the shape of
shape of the
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container,
container
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4. The components of a mixture can be separated by physical methods like handpicking, filtrations,
crystallization, distillation etc.
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5.

6. Molecules consist of different atoms or same atoms. e.g. molecule of hydrogen contains two
atoms of hydrogen whereas molecule of water contain two atoms of hydrogen and one of oxygen.

(34)
 SOME BASIC CONCEPYS OF CHEMISTRY
01

Compound is formed when two or more than two different atoms combine in fire propo e.g. water
–ration carbon dioxide, sugar etc.

7. The constituents of a compound cannot be separated by physical methods. They can only be
separate by chemical methods.
8. Physical properties are those properties which can be measured or observed without changing
the identity or the composition of the substance whereas the measurement of chemical properties
require a chemical change to occur e.g. color, odour etc. are physical properties and combustion,
basicity etc. are chemical properties.
9. The different system of measurement are English system and the metric system.
10. The SI Unit of density is Kg m-3 or kg/m3

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Short Answer:

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Ans: 1. A mole is the amount of a substance that contains as many entities (atoms, molecules, or
other particles) as there are atoms in exactly 0.012 kg or 12 g of the carbon-12 isotope.

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Ans: 2. The molarity of a solution is defined as the number of moles of the solute present per liter

a
hs
of the solution. It is represented by the symbol M. Its value changes with the change in
temperature.
at
Ans: 3. Precision and accuracy: The term precision refers to the closeness of the set of values
obtained from identical measurements of a quantity.
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Accuracy refers to the closeness of a single measurement to its true value.

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Ans: 4. Fundamental units: Fundamental units are those units by which other physical units can be
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derived. These are mass (M), Length (L), time (T), temperature (°).
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Derived units: The units which are obtained by the combination of the fundamental units are called
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derived units.
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Mole of solute
Ans: 5. Molality (m) =
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Mass of the solvent in kg

The molality of the solution does not depend upon the temperature.

Ans: 6. Atom: An atom is the smallest particle of an element that takes part in a chemical reaction.
It may or may not be capable of independent existence.
Molecule: It is the smallest particle of a substance (element or compound) that is capable of
independent existence

Ans: 7. Joule is the SI unit of work or energy

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

Long Answer:

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Ans: 1. The Law of Multiple Proportions states:

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“When two elements combine to form two or more than two chemical compounds than the
weights of one of elements which combine with a fixed weight of the other, bear a simple ratio to

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one another.

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Examples: hs
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1. Compound of Carbon and Oxygen: C and O combine to form two compounds CO and CO 2.
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In CO2 12 parts of wt. of C combined with 16 parts by wt. O.

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In CO2 12 parts of wt. of C combined with 32 parts by wt. of O.

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If the weight of C is fixed at 12 parts by wt., then the ratio in the weights of oxygen which combine
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with the fixed wt. of C (= 12) is 16: 32 or 1: 2.

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Thus, the weight of oxygen bears a simple ratio of 1: 2 to each other.

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2. Compounds of Sulphate (S) and Oxygen (O):

S forms two oxides with O, viz., SO2 and SO3

In SO2, 32 parts of wt. of S combine with 32 parts by wt. of O.

In SO3, 32 parts of wt. of S combine with 48 parts by wt. of O.

If the wt. of S is fixed at 32 parts, then’ the ratio in the weights of oxygen which combine with the
fixed wt. of S is 32: 48 or 2: 3.

Thus, the weights of oxygen bear a simple ratio of 2: 3 to each other.

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

Ans: 2. Law of Constant Composition of Definite Proportions states: “A chemical compound is always
found, to be made up of the same elements combined together in the same fixed proportion by
weight”.

Examples:

1. CO2 may be prepared in the laboratory as follows:

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In all the above examples, CO2 is made up of the same elements i. e., Carbon (C) and Oxygen (O)

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combined together in the same fixed proportion by weight of 12: 32 or 3: 8 by weight.

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hs
Ans: 3. The empirical formula of a compound expresses the simplest whole-number ratio of the atoms
of the various elements present in one molecule of the compound.
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For example, the empirical formula of benzene is CH and that of glucose is CH2O. This suggests that
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in the molecule of benzene one atom of Carbon (C) is present for every atom of Hydrogen (H).
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Similarly in the molecule of glucose (CH2O), for every one atom of C, there are two atoms of H and
one atom of O present in its molecule. Thus, the empirical formula of a compound represents only
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the atomic ratio of various elements present in its molecule.

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The molecular formula of a compound represents the true formula of its molecule. It expresses the
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actual number of atoms of various elements present in one molecule of a compound. For example,
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the molecular formula of benzene is C6H6 and that of glucose is C6H12O6. This suggests that in one
molecule of benzene, six atoms of C and 6 atoms of H are present. Similarly, one molecule of
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glucose (C6H12O6) actually contains 6 atoms of C, 12 atoms of H, and 6 atoms of O.

Relation between the empirical and molecular formula

Molecular formula = n × Empirical formula where n is an integer such as 1, 2, 3…

When n = 1; Molecular formula = Empirical formula

When n = 2; Molecular formula = 2 × Empirical formula.

The value of n can be obtained from the relation.

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

Molecular mass
n=
Empirical formula mass

The molecular mass of a volatile substance can be determined by Victor Meyer’s method or by
employing the relation.

Molecular mass = 2 × vapour density.

Empirical formula mass can however be obtained from its empirical formula simply by adding the
atomic masses of the various atoms present in it.

Thus, the empirical formula mass of glucose CH2O

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= 1 × 12 + 2 × 1 + 1 × 16 = 30.0 u.

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Ans: 4. 2 mols of HNO3 are produced by 3 mols of NO2

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𝟑 × 𝟕.𝟑𝟑
7.33 mol HNO3 are produced by mol of NO2

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𝟐

= 10.995 mols.
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Ans: 5. Molar mass of NaNO3 = 23 + 14 + 3 × 16 = 85 g mol-1
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Molarity = Number of moles of solute Volume of solution in L

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𝟎.𝟖𝟑×𝟏𝟎𝟎𝟎
=
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𝟖𝟓 ×𝟓𝟎
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= 0.196 M.
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Assertion Reason Answer:

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1. (i) Both A and R are true and R is the correct explanation of A.

2. (ii) Both A and R are true but R is not the correct explanation of A.

Case Study Answer:

1. Answer:

(1) (b) Liquid

(2) (c) Solid

(3) (c) Element

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 SOME BASIC CONCEPYS OF CHEMISTRY
01

(4) (d) Two , one.

(5) (d) Composition

2. Answer:

(1) (c) Precision

(2) (b) Antoine Lavoisier
(3) (d) 0.0052
(4) (a) Accuracy

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(5) (d) John Dalton

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CHEMISTRY

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CHAPTER 2: STRUCTURE OF ATOM

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 STRUCTURE OF ATOM
02

STRUCTURE OF ATOM

Introduction:

The word "atom" has been derived from the Greek word 'atoms’ which mans 'indivisible’. These
early ideas were mere speculation and there was no way to test them experimentally.

Atomic Structure:
Atom is made up of smaller units like proton, neutron and electron. Some other particles like

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positron, neutrino, antineutrino, π-meson, μ-meson, k meson etc are also present which are

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very short lived.

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Discovery of Electron
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In 1879, William Crooks studied the conduction of electricity through gases at low pressure. He
performed the experiment in a discharge tube which is a cylindrical hard glass tube about 60 cm
in length. It is sealed at both the ends and fitted with two metal electrodes. The electrical
discharge through the gases could be observed only at very low pressures and at very high
voltages.

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 STRUCTURE OF ATOM
02

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J.J. Thomson took a discharge tube and applied a voltage of a 10000 volt potential difference
across it at a pressure of 10–2 mm of Hg. He found some glowing behind anode. It means some

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invisible rays produced at cathode strike behind anode and produce fluorescence. He named
them cathode rays.

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Properties of Cathode Rays
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i. These rays have mechanical energy and travel in straight line.
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ii. These rays are deflected towards positive plate of electric field. It means these are made up
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of negatively charged particle called electron.

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iii. Colour observed is independent from nature of gas.

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iv. Mulliken determined the charge on electron which is 1.602 × 10-19C.

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v. Specific charge on electron is calculated by J.J. Thomson.

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Charge to mass ratio

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J.J. Thomson for the first time experimentally determined charge/mass ratio called e/m ratio
for the electrons. For this, he subjected the beam of electrons released in the discharge tube as
cathode rays to influence the electric and magnetic fields. These were acting perpendicular to
one another as well as to the path followed by electrons.

According to Thomson, the amount of deviation of the particles from their path in presence of
electrical and magnetic field depends on,

1. Magnitude of the negative charge on particle

2. Mass of particle

3. Strength of magnetic field

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 STRUCTURE OF ATOM
02

When electric field is applied, deviation from path takes place. If only electric field is applied,

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cathode rays strike at A. If only magnetic field is applied, cathode rays strike at C. In absence of

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any field, cathode rays strike at B.

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By carrying out accurate measurements on the amount of deflections observed by the
electrons on the electric field strength or magnetic field strength, Thomson was able to

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determine the value of e/me = 1.758820 x 1011 C kg-1

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where me = Mass of the electron in kg hs
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e = magnitude of charge on the electron in coulomb (C).
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Discovery of anode rays

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In 1886, Goldstein modified the discharge tube by using a perforated cathode. On reducing the
pressure, he observed a new type of luminous rays passing through the holes or perforations of
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the cathode and moving in a direction opposite to the cathode rays. These rays were named as
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positive rays or anode rays or as canal rays. Anode rays are not emitted from the anode but
from a space between anode and cathode.
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Properties of anode rays

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1. These rays deflect towards negative plate of applied electric field. It means these are
made up of positively charged particle.
2. Property of anode rays depends on nature of gas.
3. These rays travel in straight line and have mechanical energy.

Discovery of Neutron
Chadwick in 1932 found the evidence for the production of neutron in given reaction.
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4Be + 2He4 ⟶ 6C12 + 0n1

Neutron is chargeless particle and have mass equal to proton.

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 STRUCTURE OF ATOM
02

Millikan’s Oil Drop Experiment

In this experiment, some fine oil droplets were allowed to enter through a tiny hole into the
upper plate of electrical condenser. These oil droplets were produced by atomiser. The air in
the chamber was subjected to the ionization by X-rays. The electrons produced by the
ionization of air attach themselves to the oil drops.

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Thus oil droplets acquire negative charge. When sufficient amount of electric field is applied,
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the motion of the droplets can be accelerated, retarded or made stationary. Millikan observed
that the smallest charge found on them was –1.6 × 10–19 coulomb and the magnitude of
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electrical charge, q on the droplets is always an integral multiple of the electrical charge ‘e’ i.e.,
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q = ne
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Thomson’s Model of Atom

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J.J. Thomson in 1898, proposed a model of atom which looked more or less like plum pudding
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or raisin pudding. He assumed atom to be a spherical body in which electrons are unevenly
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distributed in a sphere having positive charge which balance the electron’s charge. It is called
Plum pudding model.

Important Feature of This Model: The mass of the atom is assumed to be uniformly distributed

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 STRUCTURE OF ATOM
02

over whole atom.

Failure: This model was able to explain the overall neutrality of the atom, it could not
satisfactorily, explain the results of scattering experiments carried out by Rutherford in 1911.

Rutherford's Model
Rutherford in 1911, performed some scattering experiments in which he bombarded thin foils
of metals like gold, silver, platinum or copper with a beam of fast moving a-particles. The thin
gold foil had a circular fluorescent zinc sulphide screen around it. Whenever a-particles struck
the screen, a tiny flash of light was produced at that point.

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From these experiments, he made the following observations:
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1. Most of the α-particles pass without any deviation.

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2. Few particles deviate with small angle.

3. Rare particles retrace its path or show deflection greater than 90°.
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On the basis of these observation, he proposed a model.

1. Atom is of spherical shape having size of order 10–10 meters.

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 STRUCTURE OF ATOM
02

2. Whole mass is concentrated in centre called nucleus having size of order 10–15 meters.
3. Electron revolves around the nucleus in circular path like planets revolve around sun.

Limitation: This model could not explain stability of atom. According to Maxwell's classic
theory, an accelerated charged particle liberates energy. So, during revolution, it must radiate
energy and by following the spiral path it should comes on nucleus.

Atomic number
It is equal to the number of protons present in the nucleus of an atom. Atomic number is
designated by the letter ‘Z’. In case of neutral atom atomic number is equal to the number of
protons and even equal to the number of electrons in atom.

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Z = Number of protons (p) = Number of electrons (e)

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Mass number

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It is equal to the sum of the positively charged protons (p) and electrically neutral neutrons (n).
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Mass number of an atom is designated by the letter ‘A’.
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Mass number (A) = Number of protons (p or Z) + Number of neutrons (n)
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Note: The atom of an element X having mass number (A) and atomic number (Z) may be
represented by a symbol ZXA.
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Isotopes
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Atoms with identical atomic number but different atomic mass number are known as Isotopes.
Isotopes of Hydrogen 1H1, 1H2 and 1H3
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Isobars
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Isobars are the atom with the same mass number but different atomic number, for example
14 14
6C and 7N

Electromagnetic Waves Theory

This theory was put forward by James Clark Maxwell in 1864. Electromagnetic Waves are the
waves which are produced by varying electric field and magnetic field which are perpendicular
to each other in the direction perpendicular to both of them.

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 STRUCTURE OF ATOM
02

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The main points of this theory are as follows:

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1. The energy is emitted from any source continuously in the form of radiations and is
called the radiant energy.

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2. The radiations consist of electric and magnetic fields oscillating perpendicular to each

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other and both perpendicular to the direction of propagation of the radiation.
3. The radiations possess wave character and travel with the velocity of light 3 × 108 m/sec.
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4. These waves do not require any material medium for propagation. For example, rays
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from the sun reach us through space which is a non-material medium.

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Characteristics of a Wave
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Wavelength (λ): It is the distance between two consecutive crests or troughs and is denoted by
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λ.
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Frequency (v): It is the number of waves passing through a given point in one second. The unit
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frequency is hertz or cycle per second.

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Wave number: It is the number of waves in a unit cycle. wave number =1λ=1λ

Velocity: Velocity of a wave is defined as the linear distance travelled by the wave in one
second. It is represented by c and is expressed in m/sec.

Amplitude: Amplitude of a wave is the height of the crest or the depth of the through. It is
represented by V and is expressed in the units of length.

Black Body Radiations

Black-body is an ideal body which emits and absorbs radiations of all frequencies. The radiation
emitted by these bodies is called black-body radiation.

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 STRUCTURE OF ATOM
02

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At a given temperature, the intensity and frequency of the emitted radiation depends is
temperature. At a given temperature, the intensity of radiation emitted increases with

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decrease of wavelength.

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Photoelectric Effect
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When light of a suitable frequency is allowed to incident on a metal, ejection of electrons take
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place. This phenomenon is known as photo electric effect.

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Observations in Photoelectric Effect

1. Only photons of light of certain minimum frequency called threshold frequency (v 0) can
cause the photoelectric effect. The value of v0 is different for different metals.
2. The kinetic energy of the electrons which are emitted is directly proportional to the
frequency of the striking photons and is quite independent of their intensity.
3. The number of electrons that are ejected per second from the metal surface depends
upon the intensity of the striking photons or radiations and not upon their frequency.

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 STRUCTURE OF ATOM
02

Explanation of Photoelectric Effect

Einstein in (1905) was able to give an explanation of the different points of the photoelectric
effect using Planck’s quantum theory as under:

1. Photoelectrons are ejected only when the incident light has a certain minimum frequency
(threshold frequency v0).
2. If the frequency of the incident light (v) is more than the threshold frequency (v0), the
excess energy (hv–hv0) is imparted to the electron as kinetic energy.
3. On increasing the intensity of light, more electrons are ejected but the energies of the
electrons are not altered.

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K.E. of the ejected electron.

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mv2 = hv – hv0
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Planck's Theory

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According to this theory, energy cannot be absorbed or released continuously but it is emitted
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or released in the form of small packets called quanta. In case of light this quanta is known as
photon. This photon travels with speed of light. Energy of the photon is directly proportional to
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frequency.
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E∝ν
E = hν
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h is Planck's constant, value is 6.62 × 10–34 Js

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Bohr’s Model
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1. Niels Bohr in 1913, proposed a new model of atom on the basis of Planck’s Quantum
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Theory. The main points of this model are as follows:

2. Atom is of spherical shape having size (of order 10–10 metre).
3. Whole mass is concentrated in centre called nucleus (having order of size 10–15 metre).
4. Electron revolves around nucleus only in limited circular path and he assumed that electron
does not radiate energy during its revolution in permitted paths.
5. Only those orbits are allowed whose orbit angular momentum is integral multiple
of h2πh2π.
6. mvr = nh/2π, where n = 1, 2, 3, 4...
7. When electron absorbs energy, it jumps to higher orbit and when it comes back, it radiates

(9)
 STRUCTURE OF ATOM
02

energy. This postulate explain spectra.

Achievements of Bohr’s Theory

1. Bohr’s theory has explained the stability of an atom.
2. Bohr’s theory has helped in calculating the energy of electron in hydrogen atom and one
electron species.
3. Bohr’s theory has explained the atomic spectrum of hydrogen atom.

Limitations of Bohr’s Model

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1. The theory could not explain the atomic spectra of the atoms containing more than one

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electron or multielectron atoms.
2. Bohr's theory failed to explain the fine structure of the spectral lines.

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3. Bohr’s theory could not offer any satisfactory explanation of Zeeman effect and Stark effect.

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4. Bohr’s theory failed to explain the ability of atoms to form molecule formed by chemical
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bonds.
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5. It was not in accordance with the Heisenberg’s uncertainty principle.
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Spectra
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The most compelling evidence for the quantization of energy comes from spectroscopy.
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Spectrum word is taken from Latin word which means appearance. The record of the intensity
transmitted or scattered by a molecule as a function of frequency or wavelength is called its
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spectrum.
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Cosmic rays < gamma rays < x rays < ultraviolet rays < visible rays < infra red < micro waves <
radio waves.

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 STRUCTURE OF ATOM
02

Line Spectrum of Hydrogen Atom

When electric discharge is passed through hydrogen gas enclosed in discharge tube under low
pressure and the emitted light is analysed by a spectroscope, the spectrum consists of a large
number of lines which are grouped into different series. The complete spectrum is known as
hydrogen spectrum.
On the basis of experimental observations, Johannes Rydberg noted that all series of lines in the
hydrogen spectrum could be described by the following expression:
wave number = 1λ = R(1n21 − 1n22)1λ = R(1n12 - 1n22)
R = Rydberg constant

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R = 109678 cm–1

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 STRUCTURE OF ATOM
02

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Zeeman Effect
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When spectral line (source) is placed in magnetic field, spectral lines split up into sublines. This is
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known as zeeman effect.

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Stark Effect
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If splitting of spectral lines take place in electric field, then it is known as stark effect.
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Dual Behaviour of Matter (de Broglie Equation)

De Broglie in 1924, proposed that matter, like radiation, should also exhibit dual behaviour i.e.,
both particle like and wave like properties. This means that like photons, electrons also have
momentum as well as wavelength.

Assume light have wave nature, then its energy should be given by Planck's theory

E = hνE = hν …(i)

If it have particle nature, then its energy should be given by Einstein relation,

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 STRUCTURE OF ATOM
02

E = mc2 …(ii)

On comparing equation (i) and (ii),

hν = mc2

λ = hmc (for light) …(iii)

For other matter,

λ = hmv …(iv)

λ = hp …(v)

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where p = momentum

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This equation is called de Broglie equation.

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Heisenberg’s Uncertainty Principle

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It states that, "It is impossible to measure simultaneously the exact position and exact
momentum of a microscopic particle".
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If uncertainty in position = Δ × and
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Uncertainty in momentum = ΔP

When both are measured simultaneously, According to this principle,

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Δ ×.ΔP ≥ h4π
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Quantum Numbers
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There are a set of four quantum numbers which specify the energy, size, shape and orientation
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of an orbital. To specify an orbital only three quantum numbers are required while to specify an
electron all four quantum numbers are required.

1. Principal quantum number (n): It identifies shell, determines sizes and energy of orbitals. It
is indicated by ‘n’ and its values are 1, 2, 3, 4...
2. Azimuthal quantum number (l): Azimuthal quantum number. ‘l’ is also known as orbital
angular momentum or subsidiary quantum number. l. It identifies sub-shell, determines the
shape of orbitals, energy of orbitals in multi-electron atoms along with principal quantum
number and orbital angular momentum, i.e., The number of orbitals in a sub shell = 2l + 1.
For a given value of n, it can have n values ranging from 0 to n-1.
3. Magnetic quantum number (ml): It gives information about the spatial orientation of the

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 STRUCTURE OF ATOM
02

orbital with respect to standard set of co-ordinate axis.For any sub-shell (defined by ‘l’
value) 2l+1 values of ml are possible. For each value of l, ml = – l, – (l–1), – (l–2)... 0,1...(l–2),
(l–1), l
4. Electron spin quantum number (ms): It refers to orientation of the spin of the electron. It
can have two values +1/2 and -1/2. +1/2 identifies the clockwise spin and -1/2 identifies the
anti-clockwise spin.

Shape of Atomic Orbitals

Shapes of s-orbitals: s-orbital is present in the s-sub shell. For this sub shell, l = 0 and ml = 0.
Thus, s-orbital with only one orientation has a spherical shape with uniform electron density

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along all the three axes. The probability of Is electron is found to be maximum near the nucleus
and decreases with the increase in the distance from the nucleus.

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Shapes of p-orbitals: p-orbitals are present in the p-subshell for which l = 1 and ml can have
three possible orientations –1, 0, +1. Thus, there are three orbitals in the p-subshell which are
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designated as px, py and pz orbitals depending upon the axis along which they are directed. The
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general shape of a p-orbital is dumb-bell consisting of two portions known as lobes.

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Shapes of d-orbitals: d-orbitals are present in d-subshell for which l = 2 and ml = -2, -1, 0, +1 and
+2. This means that there are five orientations leading to five different orbitals. d orbitals are of
five types: dxy, dyz, dzx, dx2-y2, dz2

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 STRUCTURE OF ATOM
02

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Electronic Configuration
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Distribution of electron in various orbitals is known as electronic configuration. The electrons
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filled in orbitals must obey the following rules-
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• Aufbau’s principle
• Pauli’s exclusion principle
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• Hund’s rule of maximum multiplicity

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1. Aufbau’s principle: According to this principle, orbitals with lowest energy are filled before
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the orbitals having higher energy.

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 STRUCTURE OF ATOM
02

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1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p
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(n + l) rule (Bohr Bury’s Rule)

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According to this, The orbital which has lower value of (n + l) is lower in energy.
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2. Pauli’s exclusion principle: According to this principle, in an atom, no two electrons have
same value of all the four quantum numbers. In the same orbital, electron always
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accommodate in opposite spins. An orbital can have a maximum of two electrons, with
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opposite spin.
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3. Hund’s rule of maximum multiplicity: According to this rule, electrons are distributed among
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the orbital of a subshell in such a way so as to give the maximum number of unpaired
electrons with a parallel spin.

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 STRUCTURE OF ATOM
02

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Discovery of Proton hs
Last Updated on July 6, 2022 By Mrs Shilpi Nagpal 3 Comments
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Since the atom as a whole is electrically neutral and the presence of negatively charged particles
in it was established ,therefore, it was thought that some positively charged particles must also
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be present in the atom.

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Goldstein in 1886 performed discharge tube experiment in which he took perforated cathode
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and a gas at low pressure was kept inside the tube, as before.
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1)On passing high voltage between the electrodes ,it was found that some rays were coming
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from the side of the anode which passed through the holes in the cathode and produced green
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fluorescence on the opposite glass wall coated with zinc sulphide. These rays were called anode
rays or canal rays or positive rays.

Properties of anode rays

1)They travel in straight line.

2)They are made up of material particles.

3)They are positively charged.

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 STRUCTURE OF ATOM
02

4)The value of e/m depend upon the nature of gas taken inside the discharge tube.

5)The value of the charge on the particles constituent the anode rays is also found to depend
upon the nature of the gas taken inside the discharge tube.

6)The mass of the particle constituting the anode rays is also found to be different for different
gases taken in discharge tube.

The charge on these particles is found to be same as that on the electron i.e. 1.6 × 10-19
coulombs per gram.

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The ratio, charge/mass, for each of the particle is found to be 9.58 × 10-24 g.

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These particles were termed as protons.

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A proton may be defined as that fundamental particle which carries 1 unit positive charge and

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has a mass nearly equal to that of hydrogen atom.
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Discovery of neutron
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Chadwick in 1932 ,performed some scattering experiment in which he bombarded some light
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elements like beryllium and boron with fast moving Alpha particles. He found that some new
particles were emitted which carried no charge ie. were neutral but had a mass nearly equal to
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that of proton. This particle was termed neutrons.

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A neutron may be defined as that fundamental particles which carries no charge but has a mass
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nearly equal to that of hydrogen atom or proton.

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Rutherford’s Model of an Atom

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Thomson’s model of atom

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 STRUCTURE OF ATOM
02

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J.J. Th

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result of the balance between the repulsive forces between the electrons and their attraction

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towards the centre of the positive Sphere.This model is compared with a watermelon in which
seeds are embedded or with a cake or pudding in which raisins are embedded. That is why this

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model is called as raisin pudding model a watermelon model.

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Limitation hs
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This model could not explain the stability of the atom.
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Rutherford Model of atom

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Rutherford in 1911, performed scattering experiment in which he bombarded thin walls of

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 STRUCTURE OF ATOM
02

metals like gold, silver, Platinum or copper with a beam of fast moving Alpha particles. The
source of Alpha particles was radium, a radioactive substance, placed in a block of lead. Slits
were used to get a fine beam. The presence of Alpha particles at any point around the thin foil
of gold after striking it was detected with the help of a circular zinc sulphide. The point at which
an Alpha particle strikes this screen ,a flash of light is given out.

Observation

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1) Most of the Alpha particles passed through the foil without undergoing any deflection.
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2) Few Alpha particles underwent deflection through small angles.

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3) Very few were deflected back through an angle greater than 90°

Conclusion

1)Since most of the Alpha particles passed through the foil without undergoing any deflection,
there must be sufficient empty space within the atom.

2)Since few alpha particles were deflected through small angles and alpha particles were
positively charged particles, these could be deflected only by some positive body present within
the atom. The alpha particles deflected were those which passed very close to this positive
body.

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 STRUCTURE OF ATOM
02

3)Since some alpha particles were deflected back and alpha particles are heavy particle, these
could be deflected back only when they strike some heavier body inside the atom.

4)Since the number of alpha particles deflected back is very very small, this shows that the
heavy body present in an atom must be occupying a very very small volume.

The small heavy positively charged body present within the atom was called nucleus.

Rutherford Model of an atom

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(1) Nucleus is very small in size, carries positive charge and in which the entire mass of the atom
is concentrated.
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(2) Since electrons have negligible mass ,the mass of the atom is mainly due to protons and
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neutrons.

(3) Protons and neutrons must be present in the nucleus.

(4) Extranuclear part is the space around the nucleus in which the electrons were distributed.

Drawback of Rutherford’s Model of an atom

(1) Inability to explain the stability of atom

An atom consists of a small, heavy positively charged nucleus in the centre and the electrons
were revolving around it. This model was compared with the solar system in which the planets

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 STRUCTURE OF ATOM
02

were revolving around the sun and continue to move in their fixed circular paths because the
force of attraction was balanced by the centrifugal force.

According to Maxwell’s electromagnetic theory, whenever a charged particle like electron is

revolving in a field of force like that of the nucleus, it loses energy continuously in the form of
electromagnetic radiation. This is because when a particle is revolving, it undergoes acceleration
due to change in direction even if the speed remains constant. Thus, the orbit of the revolving
electron will keep on becoming smaller and smaller, following a spiral path and ultimately the
electron should fall into the nucleus. The atom should collapse.

Rutherford model could not explain the stability of the atom.

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(2) Inability to explain the line spectra of the elements.

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(3) Inability to describe distribution of electrons and energies of electrons.

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Electromagnetic Wave Theory hs
Electromagnetic wave theory
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This theory was put forward by James clark Maxwell in 1864.

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The main points of this theory are:

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1)The energy is emitted from any source continuously in the form of radiations and is called the
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radiant energy.
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2)The radiations consist of electric and magnetic fields oscillating perpendicular to each other
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and both perpendicular to the direction of propagation of the radiation.

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3)The radiations possesses wave character and travel with the velocity of light.

The radiations are called electromagnetic radiations or electromagnetic waves.

4)These waves do not require any material medium for propagation.

Characteristics of a wave

1)Wavelength

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 STRUCTURE OF ATOM
02

Wavelength of a wave is defined as the distance between any two consecutive crest or trough.

It is represented by λ (Lambda) and is expressed in A° or m or cm or nm or pm.

1 A° = 10-8 cm = 10-10 m

1nm = 10-9 m, 1pm= 10-12 m

2)Frequency

Frequency of a wave is defined as the number of waves passing through a point in 1 seconds.

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It is represented by ν (nu) and is expressed in hertz(Hz) or cycles/second or sec-1

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3)Velocity

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Velocity of a wave is defined as the linear distance travelled by the wave in 1 seconds.
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It is represented by c and is expressed in cm/sec or m/sec.
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4)Amplitude
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Amplitude of a wave is the height of the crest or the depth of the trough.
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It is represented by a and is expressed in the units of length.

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5)Wavenumber
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Wavenumber is defined as the number of waves present in 1 cm length.

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It will be equal to the reciprocal of the wavelength.

It is represented by 𝑣̅

Relation between velocity ,wavelength and frequency of a wave

𝐶 = 𝜆𝑣

Electromagnetic Spectrum

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 STRUCTURE OF ATOM
02

The different types of electromagnetic radiations differ only in their wavelength and hence
frequency.

Their Wave length increases in the following order:

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Electromagnetic spectrum
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When these electromagnetic radiations are arranged in order of their increasing wavelength or
decreasing frequencies, the complete spectrum obtained is called electromagnetic spectrum.
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Limitations of electromagnetic wave theory

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It could not explain the :

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1)The phenomena of black body radiation

2)The photoelectric effect

3)The variation of heat capacity of solid as a function of temperature.

4)The line spectra of atoms with special reference to hydrogen.

Black body radiation

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 STRUCTURE OF ATOM
02

If any substance with high melting point is heated, it first becomes red, then yellow and finally
begins to glow with white and then blue light.

If the substance being heated is a black body (which is a perfect absorber and perfect radiator of
energy ie. which can emit and absorb all frequencies) the radiations emitted is called black body
radiation

The energy of any electromagnetic radiation is proportional to its intensity, ie. square of
amplitude and is independent of its frequency or wavelength.

The change of colours shows that on heating ,the frequency of the radiations emitted is

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increasing.

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Intensity versus wavelength

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At a given temperature, intensity of radiation emitted increases with decrease of wavelength,

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reaches a maximum value at a particular wavelength and then start decreasing with further
decrease of wavelength.
hs
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Photoelectric effect
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When radiations with certain minimum frequency ( νo) strike the surface of a metal, the
electrons are ejected from the surface of the metal. This phenomenon is called Photoelectric
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effect
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The electrons emitted are called photoelectrons.

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1) The electrons are ejected only if the radiation striking the surface of the metal has at least a
minimum frequency(νo) . If the frequency is less than νo , no electrons are ejected(hνo). This
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value is called threshold frequency.

The minimum energy required to eject the electrons is called work function( Wo)

2) The velocity of the electron ejected depends upon the frequency of the incident radiation and
is independent of its intensity.

3) The number of photoelectrons ejected is proportional to the intensity of incident radiation.

Planck’s Quantum Theory

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 STRUCTURE OF ATOM
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Max Planck in 1900, put forward a theory known after his name as Planck’s Quantum theory

The main points of this theory are :

1)The radiant energy is emitted or absorbed not continuously but discontinuously in the form of
small discrete packets of energy. Each such packet of energy is called quantum. In case of light
,the quantum of energy is called Photon.

2)The energy of each quantum is directly proportional to the frequency of the radiation ie.

E=hν

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Where h is the proportionality constant, called Planck’s Constant.

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Its value is 6.626 × 10 -27 erg sec or 6.626 × 10 -34 joule sec.

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3)The total amount of energy emitted or absorbed by a body will be some whole number
hs
quanta.
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Hence E= nhν
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Explanation of black body radiation

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When some solid substance is heated, the atoms of the substance are set into oscillations and
emit radiations of frequency, ν. Now ,as heating is continued, more and more energy is being
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absorbed by the atoms and they emit radiations of higher and higher frequency. As red light has
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minimum frequency and yellow light has higher frequency, therefore the body on heating
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becomes first red, then yellow and so on.

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Explanation of Photoelectric Effect

1)When light of some particular frequency falls on the surface of metal, the photon gives its
entire energy to the electron of the metal atom. The electron will be detached from the metal
atom only if the energy of the photon is sufficient to overcome the force of attraction of the
electron by the nucleus. That is why photoelectrons are ejected only when the incident light has
a certain minimum frequency (threshold frequency ν0)

2If the frequency of the incident light is more than the threshold frequency ,the excess energy is
imparted to the electron as kinetic energy.

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 STRUCTURE OF ATOM
02

Greater is the frequency of the incident light, greater is the kinetic energy of emitted electron.

3)When the intensity of light is increased, more electrons are ejected but the energies of these
electrons are not altered.

Absorption and Emission Spectra

Electromagnetic spectrum

The electromagnetic spectrum consists of radiation of different wavelength and frequency.

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An instrument used to separate the radiations of different wavelength is called spectroscope or
spectrograph.

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A spectroscope consists of a prism or a diffraction grating for the dispersion of radiation and a

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photographic film to examine the emergent radiation with the human eye.

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hs
The branch of science dealing with the study of spectra is called spectroscopy.
at
The spectra are broadly classified into:
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1) Emission spectra
ita
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2) Absorption Spectra
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Emission spectra
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When the radiations emitted from some source eg: from the sun or by passing electric discharge
through a gas at low pressure or by heating some substance to high temperature is passed
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directly through the prism and then received on the photographic plate, the spectrum obtained
is called emission spectrum.

Depending upon the source of radiation, the emission spectra are mainly of two types:

1) Continuous spectrum

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 STRUCTURE OF ATOM
02

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When white light from any source is analysed by passing through a prism, it is observed that it

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splits up into 7 different wide bands of colour. These colours are so continuous that each of

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them merges into the next. Hence the spectrum is called continuous spectrum.
hs
On passing through the prism, red colour with the longest wavelength is deviated least while
at
violet colour with shortest wavelength is deviated the most.
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2) Line Spectra
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When some volatile salt is placed in the bunsen flame or an electric discharge is passed through
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a gas at low pressure, light is emitted. The colour of light emitted depends upon the nature of
.d

substance.
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Sodium emits yellow light while potassium gives out violet light.
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If this light is resolved in a spectroscope, some isolated coloured lines are obtained on the
photographic plates separated from each other by dark spaces. This spectrum is called line
emission spectrum on line spectrum.

Each line in the spectrum corresponds to a particular wavelength. Sodium always gives two
yellow lines.

Absorption spectra

White light from any source is passed through the solution or vapours of a chemical substance
and then analysed by the spectroscope, it is observed that some dark lines are obtained. These

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 STRUCTURE OF ATOM
02

dark lines are supposed to result from the fact that when the white light is passed through the
chemical substance,, the radiations of certain wavelengths are absorbed, depending upon the
nature of the element.

The dark lines are at the same place where coloured lines are obtained in the emission spectra
for the same substance. The wavelength absorbed were same as were emitted in the emission
spectra. The spectrum thus obtained is called absorption spectrum.

Emission spectrum of Hydrogen

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a la
hs
at
lp
ita
ig
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When hydrogen gas at low pressure is taken in the discharge tube and the light emitted on
passing electric discharge is examined with a spectroscope ,the spectrum obtained is called the
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emission spectrum of hydrogen.It is found to consist of a large number of lines which are
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grouped into different series ,named after the discoverer.

Rydberg in 1890 gave a very simple theoretical equation for the calculation of wavelength of
these lines.

Where R is a constant ,called Rydberg constant and has a value of 109677 cm-1 or 1.097 × 107
m-1

n1 and n2 are whole numbers and for a particular series, n1 is constant and n2 varies .

Rydberg's constant for hydrogen

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 STRUCTURE OF ATOM
02

Where Z is the atomic number.

Summary-
1. Atomic number: It is equal to the number of protons in the nucleus of an atom.
2. Mass number: It is equal to the sum of the positively charged protons (p) and electrically
neutral neutrons (n).
3. Isotopes: Isotopes are the atoms of the same element which have the same atomic number
but different mass numbers.
4. Isobars: Isobars are the atoms of different elements having the same mass number but

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different atomic numbers.

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5. Isoelectronic species: These are those species which have same number of electrons.
6. Radiations: These are defined as the emission or transmission of energy through space in

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the form of waves.

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7. Electromagnetic waves: The waves which consist of oscillating electric and magnetic fields
hs
are called electromagnetic waves.
at
8. Electromagnetic radiations: Those radiations which are associated with electric and
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magnetic field are called electromagnetic radiations.

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9. Electromagnetic spectrum: The arrangement of the various types of electromagnetic

radiations in the order of increasing or decreasing wavelengths or frequencies is known as
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electromagnetic spectrum.
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10. Wavelength (λ): It is the distance between successive points of equal phase of a wave.
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11. Frequency (f): The number of waves that pass a given point in one second is known as the
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frequency.
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12. Time period (T): Time taken by the wave for one complete cycle or vibration is called time
period.
13. Velocity (v): It is the distance travelled by a wave in one second.
14. Wave number: It is defined as the number of wavelengths per unit length.
15. Threshold frequency: It is the minimum frequency of light needed to cause the
photoelectric effect.
16. Continuous spectrum: The combination of light of different frequencies in continuous
manner is called continuous spectrum.
17. Line spectrum: The spectrum of atoms consist of sharp well-defined lines corresponding to
definite frequencies is called line spectrum.

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 STRUCTURE OF ATOM
02

18. Spectroscopy: The study of emission or absorption spectra is called spectroscopy.

19. Quantization: The restriction of a property to discrete values and not continuous values is
called quantization.
20. Quantum mechanics: The branch of science that takes into account the dual behaviour of
matter is called quantum mechanics.
21. Atomic orbital: It is the region of space where the probability of finding the electron is
maximum.
22. Quantum numbers: may be defined as a set of four numbers with the help of which we can
get complete information about electron in an atom.

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STRUCTURE OF ATOM

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STRUCTURE OF ATOM

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 STRUCTURE OF ATOM
02

Important Questions
Multiple Choice questions-
Question 1. Which of the following pair of ions have same paramagnetic moment?
(a) Cu+2, Ti+3
(b) Mn+2, Cu+2
(c) Ti+4, Cu+2
(d) Ti+3, Ni+2
Question 2. The charge to mass ratio of α – particles is approximately …… the charge to mass

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ratio of protons

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(a) Twice

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(b) Half

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(c) Four times

a
(d) Six times hs
Question 3. The frequency of a wave of light is 12 × 1014s-1. The wave number associated with
at
this light
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(a) 5 × 10-7m
(b) 4 × 10-8cm-1
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(c) 2 × 10-7m-1
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(d) 4 × 104cm-1
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Question 4. In a multi – electron atom, which of the following orbitals described by the three
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quantum numbers will have the same energy in the absence of magnetic acid and electric fields?
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(a) n = 1, l = 0, m = 0 (b) n = 2, l = 0, m = 0 (c) n = 2, l = 1, m = 1 (d) n = 3, l = 2, m = 1 (e) n = 3, l = 2,

m=0
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(a) (a) and (b)

(b) (b) and (c)
(c) (c) and (d)
(d) (d) and (e)
Question 5. The electronic transitions from n = 2 to n = 1 will produce shortest wavelength in
(where n = principal quantum state)
(a) Li2+
(b) He+
(c) H

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 STRUCTURE OF ATOM
02

(d) H+
Question 6. In a hydrogen atom, if energy of an electron in ground state is 13.6 eV, then that in
the 2nd excited state is
(a) 1.51 eV
(b) 3.4 eV
(c) 6.04 eV
(d) 13.6 eV
Question 7. The credit of discovering neutron goes to

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(a) Rutherford

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(b) Thomson

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(c) Goldstein
(d) Chadwick

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Question 8. The maximum number of electrons that can be accommodated in fifth energy level
is hs
(a) 10
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(b) 25
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(c) 50
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(d) 32
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Question 9. According to Aufbaus principle, which of the three 4d, 5p and 5s will be filled with
electrons first
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(a) 4d
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(b) 5p
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(c) 5s
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(d) 4d and 5s will be filled simultaneously

Question 10. A hydrogen atom in its ground state absorbs 10.2 eV of energy. The orbital angular
momentum is increased by (Given Planck constant h = 6.6 × 10-34 Jsec)
(a) 1.05 × 10-34 Jsec
(b) 3.16 × 10-34 Jsec
(c) 2.11 × 10-34 Jsec
(d) 4.22 × 10-34 Jsec
Question 11. The ionization enthalpy of hydrogen atom is 1.312 × 106 J mol-1. The energy
required to excite the electron in the atom from n = 1 to n = 2 is

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 STRUCTURE OF ATOM
02

(a) 8.51 × 105 Jmol-1

(b) 6.56 × 105 Jmol-1
(c) 7.56 × 105 Jmol-1
(d) 9.84 × 105 Jmol-1/sup>
Question 12. For principal quantum number n = 4, the total number of orbitals having l = 3 is
(a) 3
(b) 7
(c) 5

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(d) 9

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Question 13. Maximum number of electrons in a subshell with l = 3 and n = 4 is

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(a) 10

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(b) 12

a
(c) 14
(d) 16
hs
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Question 14. Which hydrogen-like species will have same radius as that of Bohr orbit of
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hydrogen atom?
(a) n = 2, Li2+
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(b) n = 2, Be3+
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(c) n = 2, He+
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(d) n = 3, Li2+
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Question 15. The magnetic quantum number specifies

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(a) Size of orbitals

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(b) Shape of orbitals

(c) Orientation of orbitals
(d) Nuclear Stability

Very Short:
1. How many total electrons are present in nitrate ion?
2. The nucleus of the atom of an element does not contain a neutron. Name the element and
what does its nucleus consists of.
3. What are nucleons?

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 STRUCTURE OF ATOM
02

4. Write electronic configurations of Chromium (At. Np. = 24).

5. Which of the following has the smallest de-Broglie wavelength? O2, H2, a proton, an
electron
6. How many unpaired electrons are there is a carbon atom in the ground state?
7. What type of spectrum is obtained when light emitted from the discharge tube containing
hydrogen gas is analyzed?
1
8. What is the maximum number of electrons in an atom having n = 3, l = 1 and s = + ?
2
9. Name the spectral line in the spectrum of H-atom obtained when an electron jumps from n
= 4 to n = 2.

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10. Give some examples of electromagnetic radiation.

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Short Questions:

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1. Enumerate the important characteristics of anode-rays (or positive rays). How this study

a
led to the discovery of proton?
2.
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What are anode-rays? Illustrate their formation by a diagram.
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3. Describe the important properties of cathode-rays. What is concluded about the nature of
these rays?
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4. What are the main features of Rutherford’s model of an atom?

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5. What is meant by the dual nature of radiation?

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6. Describe the drawback to Rutherford’s model of the atom.

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7. What is the value of?

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(i) Charge to mass ratio (e/m) of electrons,

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(ii) Charge of electrons,

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(iii) Mass of an electron?

Long Questions:
1. Describe the shape of s – and p – orbitals What do you mean by node or nodal surface?
2. How does the Schrodinger wave equation help to understand the probability of finding the
electron near the nucleus? What do you mean by an orbital?
3. How many nucleons are present in an atom Nobelium, No? How many electrons are present
in the atom? How many nucleons may be considered neutrons?
4. Complete the following table:

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 STRUCTURE OF ATOM
02

5. Find the number of protons, electrons an-d neutrons in (a) 1327A3+

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Assertion Reason Questions:

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1. In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is

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given. Choose the correct option out of the choices given below each question.

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Assertion (A) : All isotopes of a given element show the same type of chemical

a
behaviour.
hs
Reason (R) : The chemical properties of an atom are controlled by the
at
number of electrons in the atom.
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(i) Both A and R are true and R is the correct explanation of A.

(ii) Both A and R are true but R is not the correct explanation of A.
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(iii) A is true but R is false.

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(iv) Both A and R are false.

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2. In the following questions, a statement of Assertion (A) followed by a statement of Reason (R) is
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given. Choose the correct option out of the choices given below each question.
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Assertion (A) : Black body is an ideal body that emits and absorbs radiations
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of all frequencies.
Reason (R) : The frequency of radiation emitted by a body goes from a lower
frequency to higher frequency with an increase in
temperature.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the explanation of A.
(iii) A is true and R is false.
(iv) Both A and R are false.

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 STRUCTURE OF ATOM
02

Case Study Based Question:

1. The atomic theory of matter was first proposed on affirm scientific basis by John Dalton, a
British schoolteacher in 1808. His theory, called Dalton’s atomic theory, regarded the atom as
the ultimate particle of matter Dalton’s atomic theory was able to explain the law of
conservation of mass, law of constant composition and law of multiple proportion very
successfully. However, it failed to explain the results of many experiments. In mid 1850s many
scientists mainly Faraday began to study electrical discharge in partially evacuated tubes,
known as cathode ray discharge tubes. Electrical discharge carried out in the modified cathode
ray tube led to the discovery of canal rays carrying positively charged particles. The
characteristics of these positively charged particles are listed below.

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1) Unlike cathode rays, mass of positively charged particles depends upon the nature of
gas present in the cathode ray tube. These are simply the positively charged gaseous ions.

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2)The charge to mass ratio of the particles depends on the gas from which these originate.

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3) Some of the positively charged particles carry a multiple of the fundamental unit of

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electrical charge.
hs
4) The behaviour of these particles in the magnetic or electrical field is opposite to that
at
observed for electron or cathode rays.
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The smallest and lightest positive ion 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
ita

electrically neutral particle as one of the constituent of atom. These particles were discovered
by Chadwick (1932)by bombarding a thin sheet of beryllium byα-particles. When electrically
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neutral particles having a mass slightly greater than that of protons were emitted. He named
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these particles as neutrons. J. J. Thomson, in 1898, proposed that an atom possesses a spherical
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shape (radius approximately 10–10 m) in which the positive charge is uniformly distributed. The
electrons are embedded into it in such a manner as to give the most stable electrostatic
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arrangement Many different names are given to this model, for example, plum pudding, raisin
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pudding or watermelon. This model can be visualised as a pudding or watermelon of positive

charge with plums or seeds (electrons)embedded into it. An important feature of this model is
that the mass of the atom is assumed to be uniformly distributed over the atom. Rutherford
and his students (Hans Geiger and Ernest Marsden) bombarded very thin gold foil with α–
particles. Rutherford’s famous α–particle scattering experiment. The observations of Scattering
experiment are as follows-:
(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 nearly
180°.

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 STRUCTURE OF ATOM
02

On the basis of observations and conclusions from this experiment, Rutherford proposed the
nuclear model of atom. According to this model:
(i) The positive charge and most of the mass of the atom was densely concentrated in
extremely small region. This very small portion of the atom was called nucleus by
Rutherford.
(ii) The nucleus is surrounded by electrons that move around the nucleus with a very high
speed in circular paths called orbits. Thus, Rutherford’s model of atom resembles the solar
system in which the nucleus plays the role of sun and the electrons that of revolving
planets.

)
(iii) Electrons and the nucleus are held together by electrostatic forces of attraction.

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1) The atomic theory of matter was first proposed on affirm scientific basis by.

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(a) John Dalton

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(b) Ernest Rutherford

a
(c) J. Thomson hs
(d) Henry Moseley
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2) The cathode rays start from ……..… and move towards the ………….
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(a) Anode , Cathode

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(b) Centre , Anode

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(c) Cathode , Anode

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(d) Cathode , Centre

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3) Negatively charged particles in atoms , called …….…

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(a) Protons
(b) electrons
(c) Neutron
(d) Positron
(4) The smallest and lightest positive ion was obtained from ……….. and was called proton.
(a) Oxygen
(b) Nitrogen
(c) Carbon

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 STRUCTURE OF ATOM
02

(d) Hydrogen
(5) Electrically neutral particles having a mass slightly greater than that of protons, these
particles termed as …………
(a) Protons
(b) electrons
(c) Neutron
(d) Positron
2. The presence of positive charge on the nucleus is due to the protons in the nucleus. As

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established earlier, the charge on the proton is equal but opposite to that of electron. Atomic
number (Z) = number of protons in the nucleus of an atom = number of electrons in a neutral

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atom. protons and neutrons present in the nucleus are collectively known as nucleons. The total
number of nucleons is termed as mass number (A) of the atom.

la
mass number (A) = number of protons (Z) + number of neutrons (n).

a
hs
Isobars are the atoms with same mass number but different atomic number for example, 614C
and 714N. On the other hand, atoms with identical atomic number but different atomic mass
at
number are known as Isotopes. For example, considering of hydrogen atom again, 99.985%of
lp

hydrogen atoms contain only one proton. This isotope is called protium (1 1H). Rest of the
percentage of hydrogen atom contains two other isotopes, the one containing 1 proton and
ita

1neutron is called deuterium (21D, 0.015%)and the other one possessing 1 proton and
2neutrons is called tritium (13T )..the studies of interactions of radiations with matter have
ig

provided immense information regarding the structure of atoms and molecules. Niels
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Bohrutilised these results to improve upon the model proposed by Rutherford. Two
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developments played a major role in the formulation of Bohr’s model of atom. These were:
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(i) Dual character of the electromagnetic radiation which means that radiations possess
both wave like and particle like properties, and
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(ii) Experimental results regarding atomic spectra.

James Maxwell (1870) was the first to give a comprehensive explanation about the interaction
between the charged bodies and the behavior of electrical and magnetic fields on macroscopic
level. He suggested that when electrically charged particle moves undercalculation, alternating
electrical and magnetic fields are produced and transmitted. These fields are transmitted in the
forms of waves called electromagnetic waves or electromagnetic radiation. radiations are
characterised by the properties, namely, frequency (ν ) and wavelength (λ).The SI unit for
frequency (ν) is hertz(Hz, s–1), after Heinrich Hertz. It is defined as the number of waves that
pass a given pointing one second. Wavelength should have the units of length and as you know
that the SI units of length is meter (m). Since electromagnetic radiation consists of different

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 STRUCTURE OF ATOM
02

kinds of waves of much smaller wavelengths, smaller units are used. In vacuum all types of
electromagnetic radiations, regardless of wavelength, travel at the same speed, i.e., 3.0 × 108m
s–1 (2.997925× 108 ms–1, to be precise). This is called speed of light and is given the symbol ‘c‘.
The frequency (ν ), wavelength (λ) and velocity of light(c) are related by the following equation .
c=νλ
The other commonly used quantity specially in spectroscopy, is the wavenumber. It is defined
as the number of wavelengths per unit length. Its units are reciprocal of wavelength unit, i.e.,
m–1. However commonly used unit is cm–1
1) The presence of positive charge on the nucleus is due to the …………. in the nucleus.

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(a) Protons

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(b) Neutrons
(c) Electron

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(d) Nucleons

a
2) Atomic Number is denoted by …………
hs
at
(a) A
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(b) Z
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(c) N
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(d) M
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3) Atomic Mass number is denoted by …………..

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(a) M
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(b) Z
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(c) N
(d) A
4) ………… are the atoms with same mass number but different atomic number.
(a) Isotopes
(b) Allotropes
(c) Isobars
(d) None of above
5) Atoms with identical atomic number but different atomic mass number are known as ..

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 STRUCTURE OF ATOM
02

(a) Isotopes
(b) Allotropes
(c) Isobars
(d) None of above

Answer Key:
MCQ

)
1. (a) Cu+2, Ti+3

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2. (b) Half

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3. 4 × 104cm-1

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4. (d) (d) and (e)

a
5. (a) Li2+
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6. (a) 1.51 eV
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7. (d) Chadwick
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8. (c) 50
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9. (9) 5s
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10.(a) 1.05 × 10-34 Jsec

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11.(d) 9.84 × 105J mol-1

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12.(b) 7

13.(c) 14

14.(b) n = 2, Be3+

15.(c) Orientation of orbitals

Very Short Answer:

1. No. of electrons in NO3– ion
= No. of electrons on N + No. of electrons on 3 oxygen atoms + one ē
= 7 + 3 × 8 + 1 = 32 electrons.

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 STRUCTURE OF ATOM
02

2. The nucleus of hydrogen. It contains only one proton.

3. The neutrons and protons present in the nucleus of an atom are collectively called nucleons.

4. Cr = 24 = 1s2, 2s2 2p6, 3s2 3p6 3d5, 4s1.

h 1
5. According to the de-Broglie equation λ = for same value of velocity λ ∝
m×v m

∴ O2 molecule has shortest wavelength.

6. C = 6 = 1s2, 2s2, 2p1x 2p1y. There are only two unpaired electrons.

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7. Emission line spectrum.

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8. Three electrons (one each in 3px’ 3py’, 3pz’).

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9. Balmer Series.

a
hs
10. Y-rays, X-rays, UV-rays, visible rays, radio waves, etc.
at
Short Answer:
lp

Ans: 1. The mass of positive particles which constitute these rays depend upon the nature of the
ita

gas in the tube. The charge/mass (e/m) ratio of anode-rays is not constant but depends upon the
nature of gas in the tube. The value of e/m is greatest for the lightest gas, hydrogen the electric
ig

charge on a lightest positively charged particle from hydrogen gas was found to be exactly equal
.d

in magnitude but opposite in sign to that of the electron. This lightest positively charged particle
w

from hydrogen gas was named the proton. The mass of a proton is almost 1836 times that of the
electron.
w
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Ans: 2. Anode-rays. If a perforated cathode is used in the discharge tube experiment, it is found
that a certain type of radiation also travels from anode to cathode. These are called anode rays
or positive rays.

(44)
 STRUCTURE OF ATOM
02

Production of anode rays

)
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Ans: 3. The cathode rays possess the following properties:

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1. Travel in straight lines perpendicular to the surface of the cathode.

la
2. Consists of material particles.
3. Have got the heating effect.

a
4.
5.
Consists of negatively charged particles.hs
Produce X-rays when they strike against hard metals like copper, tungsten, platinum, etc.
at
6. Produce fluorescence when they strike glass or certain other materials like zinc sulfide.
lp

7. Penetrate through thin aluminum foils and other metals.

8. Affect the photographic plates.
ita

Ans: 4. The main features of this model are:

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1. Atom is spherical and consists of two parts: Nucleus and extra-nuclear part.
w

2. The entire mass and entire positive charge are concentrated in a very small region at the
w

center known as the nucleus.

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3. The space surrounding the nucleus known as the extra-nuclear part is negatively charged
so an atom as a whole is neutral.

4. Most of the extra-nuclear part is empty.

5. The electrons are not stationary but are revolving around the nucleus at very high speeds
like planets revolving around the Sun.

Ans: 5. The fact that light energy is carried in terms of packets of energy (i.e., photons) as
suggested by Planck’s theory means that light has a particle character. At the same time, the fact
light has a wave character. These experimental facts led Einstein to suggest that light has a dual
character, i.e., it behaves both like a wave and like a particle.

(45)
 STRUCTURE OF ATOM
02

Ans: 6. The main drawback is that it could not explain the stability of an atom. Maxwell has
shown that when electric charge is subjected to acceleration, it emits energy in the form of
radiations. In Rutherford’s model of the atom, electrons are orbiting the nucleus and hence the
direction of their velocity is constantly changing, i.e., electrons are accelerating.
This will cause the electrons will have lesser and lesser energy and will get closer and closer to
the nucleus until at last, it spirals into the nucleus and thus does not provide a stable model of
the atom.

)
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la
Ans: 7. J. Thomson determined the value of e/m for electron by the study of deflection of
electron beam under the simultaneous influence of electric and magnetic field perpendicular to

a
hs
each other, the e/m value is 1.76 × 108 coulomb per gram of electrons
at
The charge of electrons was measured by Millikan in 1909 by his famous ‘oil drop’ experiment. It
was found to be 1.60 × 10-19 coulombs.
lp
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The mass of electrons is 9.1 × 10-28 g.

Long Answer:
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Ans: 1. Shapes of Orbitals:

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s-orbitals: These are spherically symmetrical and non-directional. Shapes of 1s and 2s orbitals
w

are shown in Fig. The effective volume of 2s orbital is larger than is orbital. Another important
(w

feature of 2s orbital is that there is a spherical shell within 2s (region without dots) where the
probability of finding the electron is zero. This is called a node or a nodal surface. There are (n
- 1) nodes in an s-orbital (where n is the energy level).

p-orbitals: There are three p-orbitals designated as px’, py’ or pz’ which are oriented along

(46)
 STRUCTURE OF ATOM
02

the three mutually perpendicular axis x, y, and 2. Each, orbital consists of two lobes
symmetrical about the particular axis and has a dumbbell shape. The two lobes are
separated by a nodal plane.

)
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Shapes of three 2p orbitals

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The two lobes of each orbital are separated by a plane having x zero electron density. This
plane is known as a nodal plane.

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Ans: 2. Probability Picture of Electrons:
hs
at
Schrodinger incorporated the requirements of the uncertainty principle and de Broglie’s concept
lp

of matter waves and proposed a mathematical equation to describe the behavior of an

electron in an atom. The equation was known as the Schrodinger wave equation.
ita

The Schrodinger wave equation is

ig
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w
w

where x, y, and z are three space coordinates,

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m is the mass of the electron,

h is Planck’s, constant

E is the total energy and V is the potential energy of the electron, φ (Greek letter psi) is the
∂2ψ
amplitude of the wave, called wave function, refers to the second derivative of φ with
∂x2
respect to x only and so on.

The solution of this equation gave the mathematical expression which gives information
about the various energy states and other measurable properties such as the radiation
frequencies emitted or absorbed for the hydrogen atom. The solutions of the Schrodinger

(47)
 STRUCTURE OF ATOM
02

wave equation are called wave functions and are denoted by the symbol φ.

The physical significance of wave function: In the physical sense φ gives the amplitude of the
wave associated with the electron. We know that in the case of light waves, the square of
the amplitude, of the wave at a point is proportional to the intensity of light. Extending
the same concept of electron wave motion, the square of the wave function, φ2 may be
taken as the intensity of electrons at any point.

In other words, φ2 determines the probability density. Thus, φ2 has been called the
probability density and φ the probability amplitude. Thus, the solutions of the Schrodinger
wave equation replace the discrete energy levels or orbits proposed by Bohr and led to

)
the concept of the most probable regions in space in terms of φ22.

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A large value of φ2 means a high probability of finding the electron at that place and a small

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value of φ2 means low probability. If φ2 is almost zero at a particular point, it means that
the probability of finding the electron at that point is negligible. Therefore, the wave

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mechanics approach gives meaningful wave functions which describe the position and

a
energy levels of electrons in an atom. hs
Concept of Orbital: An orbital is a region in space around the nucleus where the probability of
at
finding the electrons is maximum.
lp

Ans: 3. Nucleons = 254, electrons = 102 and neutrons 254 - 102 = 152.
ita

Ans: 4.
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Ans: 5.

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 STRUCTURE OF ATOM
02

Assertion Reason Answer:

1. (i) Both A and R are true and R is the correct explanation of A.

2. (ii) Both A and R are true but R is not the explanation of A.

)
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Case Study Answer:

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1. Answer:

a la
(1) (a) John Dalton
(2) (c) Cathode, Anode
hs
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(3) (b) electrons
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(4) (d) Hydrogen

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(5) (c) Neutron

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2. Answer:
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(1) (a) Protons

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(2) (b) Z
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(3) (d) Z
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(4) (c) Isobars

(5) (a) Isotopes

(49)
 CHEMISTRY

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CHAPTER 3: CLASSIFICATION OF ELEMENTS AND PERIODICITY IN
PROPERTIES

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

CLASSIFICATION OF ELEMENTS AND

PERIODICITY IN PROPERTIES

Introduction:

Classification of elements was proposed in order to study all the elements in a systematic
manner. In this Unit, we shall study 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).

m
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Why Do We Need Classification?

la
Elements are the basic units of all types of matter. At present, 118 elements are known. With
such a large number of elements, it is very difficult to study individually the chemistry of all these

a
elements and their number of compounds. So to make the study of chemistry simpler, scientists
hs
searched for a systematic way to organise their knowledge by classifying the elements. Main aim
at
behind this classification was to keep the elements of same properties together, so that by
studying one element out of that group, we can have general idea about the properties of all the
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elements in that group.

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Periodic Table
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Periodic table may be defined as the tabular arrangement of elements in such a way that the
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elements having same properties are kept together.

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Dobereiner’s Triads Law

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1st attempt towards the classification of elements was made by Johann W. Dobereiner in 1817.
He arranged elements in the groups of three and in such a way that the atomic weight of
middle element was equal or nearly equal to the average of atomic weights of other two
elements.

ELEMENTS SYMBOL ATOMIC MASS

Lithium Li 6.9
1
Sodium Na 23

(1)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

Potassium K 39
Calcium Ca 40.1

2 Strontium Sr 87.6
Barium Ba 137.3
Chlorine Cl 35.5

3 Bromine Br 79.9
Iodine I 126.9

)
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Drawback: Only limited triads were arranged in this pattern.

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Newland’s Law of Octaves

la
In 1865, John Newland observed that in a series of elements arranged in the increasing order of

a
atomic weights, 1st and 8th elements have same properties. Now, a days, 1st and 9th elements
hs
have same properties in that series because noble gases were discovered late.
at
lp
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w
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Mendeleev’s Periodic Table

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“The physical and chemical properties of elements are a periodic function of atomic weights”.

Mendeleev arranged elements in horizontal rows and vertical columns of a table in order of
their increasing atomic weights in such a way that the elements with similar properties
occupied the same vertical column or group. Vertical Colums are called groups which are
numbered I to VIII group, each group is further subdivided into sub groups A and B. Horizontal
rows are called periods.

(2)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

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Defects in Mendeleev’s Table-

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i. Position of hydrogen: Position of hydrogen was not justified.

ii. Position of isotope: Isotopes should be placed separately according to periodic law. But
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actually one place was given to all isotopes of an element.

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iii. Cause of periodicity: Mendeleev could not explain why elements exhibit a periodicity in
w

their properties when arranged in the order of increasing atomic weight.

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iv. Anomalous pairs of elements: Some anomalous pairs were present in table. As Tellurium
(w

(128 u) comes in VI group before Iodine (127 u).

Moseley’s Peri
“The physical and chemical properties are the periodic function of their atomic numbers”.
The long form of periodic table, also called Modem Periodic Table, is based on Modern periodic
law. In this table, the elements have been arranged in order of increasing atomic numbers.
A modern version, the so-called “long form” of the Periodic Table of the elements, is the most
convenient and widely used. The horizontal rows are called periods and the vertical columns,
groups. Elements having similar outer electronic configurations in their atoms are arranged in
vertical columns, referred to as groups or families. According to the recommendation of
International Union of Pure and Applied Chemistry (IUPAC), the groups are numbered from 1 to

(3)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

18 replacing the older notation of groups IA … VIIA, VIII, IB … VIIB and 0.

There are altogether seven periods. The period number corresponds to the highest principal
quantum number (n) of the elements in the period. The first period contains 2 elements. The
subsequent periods consists of 8, 8, 18, 18 and 32 elements, respectively. The seventh period is
incomplete and like the sixth period would have a theoretical maximum of 32 elements. In this
form of the Periodic Table, 14 elements of both sixth and seventh periods (lanthanoids and
actinoids, respectively) are placed in separate panels at the bottom.

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a la
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The IUPAC names are derived by using roots for three digit atomic number of the elements.
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(4)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

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a la
hs
at
lp
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A systematic nomenclature be derived directly from the atomic number of the element using
the numerical roots for 0 and numbers 1-9. The roots are put together in order of digits which
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make up the atomic number and “ium” is added at the end. The IUPAC names for elements
.d

with Z above 100 are shown below:

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(5)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

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a la
hs
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Division of Elements into Blocks

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s-block: The elements of Group 1 (alkali metals) and Group 2 (alkaline earth metals) which
have ns1 and ns2 outermost electronic configuration belong to the s-Block Elements.
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Characteristics of s-Block elements,

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i. Except Be and Mg, all impart characteristic colour to the flame.

ii. These have low ionisation energy.
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iii. These are highly reactive.

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iv. These are the highly electropositive elements.

v. All the elements are soft metals.
vi. They have low melting and boiling points.

p-block: The p-Block Elements comprise those belonging to Group 13 to 18 and these together
with the s-Block Elements are called the Representative Elements or Main Group Elements. The
outermost electronic configuration varies from ns2np1 to ns2np6 in each period.

Characteristics of p-Block elements,

1. The compounds of p-block elements are generally covalent although their ionic character
increases down the group.
2. From left to right 13 to 18, reducing character decreases.
(6)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

3. The p-block elements generally show more than one oxidation state.
4. The reactivity of elements in a group generally decreases downwards.
5. At the end of each period is a noble gas element with a closed valence shell ns 2 np6
configuration.

d-block: These are the elements of Group 3 to 12 in the centre of the Periodic Table. These are
characterised by the filling of inner d orbitals by electrons and are therefore referred to as d-
Block Elements. These elements have the general outer electronic configuration (n-1)d1-10ns0-2.

Characteristics of d-Block elements:

)
1. They are all metals with high melting and boiling points.

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2. The compounds of the elements are generally paramagnetic in nature.

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3. They mostly form coloured ions, exhibit variable valence (oxidation states).
4. They are of tenly used as catalysts.

la
5. These elements have high melting point.

a
hs
f-block: The two rows of elements at the bottom of the Periodic Table, called the Lanthanoids,
Ce(Z = 58) – Lu(Z = 71) and Actinoids, Th(Z=90) – Lr (Z=103) are characterised by the outer
at
electronic configuration (n-2)f1-14(n-1)d0–1ns2. The last electron added to each element is filled
lp

in f-orbital. These two series of elements are hence called the Inner-Transition Elements (f-
Block Elements).
ita

Characteristics of f-Block elements:

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1. All actinoids are radioactive. Elements after uranium are known as transuranium element.
2. They form coloured compounds.
w

3. These two series of elements are called Inner Transition Elements (f-Block Elements).
w

4. They are all metals. Within each series, the properties of the elements are quite similar.
(w

5. They generally have high melting and boiling points.

Periodic Properties
The properties which generally have a regular trend along a group or period are called periodic
properties. These are as given below:

• Atomic size
• Ionisation energy
• Electron gain enthalpy
• Electronegativity

i. Atomic Size: Atomic Radius is the distance from the centre of the nucleus to the outermost

(7)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

shell containing electron.

Ionic Radius: The ionic radii can be estimated by measuring the distances between cations
and anions in ionic crystals. In general, the ionic radii of elements exhibit the same trend as
the atomic radii.

Cation: The removal of an electron from an atom results in the formation of a cation. The
radius of cation is always smaller than that of the atom.

Anion: Gain of an electron leads to an anion. The radius of the anion is always larger than
that of the atom.

)
ii. Ionisation energy: It is the amount of energy required to remove the outer most electron

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from an isolated atom in its gaseous state. It is the measured in the unit of kJ/mole. It is

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denoted by (∆iH).

M(g) - e- ⟶ M+(g)

a la
iii. Electron gain enthalpy: It is the enthalpy change when an electron is added to the gaseous
hs
neutral atom. Electron gain enthalpy provides a measure of the ease with which an atom
adds an electron to form anion. It is the measured in the unit of kJ/mole. It is denoted by
at
(∆egH).
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X(g) + e- ⟶ X-(g)
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iv. Electronegativity: Electronegativity is a measure of the tendency of an element to attract

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bonded electron pair towards itself in a covalently bonded molecule.

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Periodic Trends in Chemical Properties along a Period

w
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1. Metallic character: It decreases across a period, maximum on the extreme left (alkali
metals).
(w

2. Non-metallic character: It increases along a period, from left to right.

3. Atomic Size: It decreases across a period.

4. Ionisation energy: It increases along a period.

5. Electron gain enthalpy: It increases along a period.

6. Electronegativity: It increases along a period.

7. Basic nature of oxides: It decreases from left to right in a period.

8. Acidic nature of oxides: It increases from left to right in a period.

(8)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

Variation in Chemical Properties along a Group

1. Metallic character: Generally increases because increase in atomic size and hence decrease
in the ionizatiorn energy of the elements in a group from top to bottom.

2. Non-metallic character: It generally decreases down a group. As electronegativity of

elements decreases from top to bottom in a group.

3. Atomic Size: It increases along a group.

4. Ionisation energy: It decreases across a period.

)
5. Electron gain enthalpy: It decreases across a period.

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6. Electronegativity: It decreases across a period.

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7. Basic nature of oxides: Since metallic character or electropositivity of elements increases in

la
going from top to bottom in a group basic nature of oxidise naturally increases.

a
hs
8. Acidic character of oxides: It generally decreases as non-metallic character of elements
decreases in going from top to bottom in a group.
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9. Reactivity of metals: It generally increases down a group. Since tendency to lose electron
lp

increases.
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Historical Development Of Periodic Table

Periodic table may be defined as the table which classified all the known elements in accordance
with their properties in such a way that elements with similar properties are grouped together in
the same vertical column and dissimilar elements are separated from one another.

(9)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

Doebereiner’s Triad

)
The first attempt towards the classification of elements was made by Johann Wolfgang

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Doebereiner, a German chemist in 1817.

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He arranged similar elements in groups of three and showed that their atomic weights were
either nearly the same or the atomic weight of the middle element was approximately the

la
arithmetic mean of the other two. These group of three elements were called Doebereiner’s

a
Triads and this generalisation was called Law of triads.
hs
Drawback
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The concept of triads could be applied only to a limited number of elements.
lp
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Newlands’s law of octaves

In1865 ,an English chemist, John Alexander Newlands’s observed at that:

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When the lighter elements were arranged in order of their increasing atomic weights ,the
properties of every 8th elements were similar to those of first one like the eighth note of a
w

musical scale.This is called as Newlands’s law of octaves.

w

Drawback
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1) It was applicable to only lighter elements having atomic weights up to 40 u.

2) With the discovery of noble gases, the properties of the 8th element were no longer similar to
those of the first one.

Lothar Meyer arrangement

(10)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

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In 1869, Lothar Meyer ,a German chemist, studied the physical properties of various element.
ita

He Plotted a graph between the atomic volume and atomic weights of the elements and
observed that the elements with similar properties occupied similar position on the curve.
ig

1) The most strongly electropositive alkali metal occupy the peaks on the curve.
.d
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2) The less strongly electropositive alkaline earth metals occupy the descending position on the
curve.
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3) The most electronegative elements i.e. halogens occupy the ascending position on the curve.

Lothar Meyer proposed that the physical properties of the elements are a periodic function of
the atomic weights.

He arranged the elements in the tabular form in order of their increasing atomic weights.

Electronic configuration Of Elements

(1) The names are derived directly from the atomic numbers using numerical root for 0 and
numbers from 1-9 and adding the suffix ium. The roots for the numbers 0-9 are:

(11)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

(2) In certain cases, the names are shortened.bi ium and tri ium are shortened to bium and trium
and enn nil shortened to ennil.

(3) The symbol of the element is then obtained from the first letters of the roots of numbers
which make up the atomic number of the element.

An electron in an atom is characterised by a set of four Quantum numbers( n, l, m and s) and the
Principal quantum number (n) defines the main energy level known as the shell.

)
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Location of any element in the periodic table tells us the quantum number( n and l) of the last

.co
orbital filled.

la
Electronic configuration of elements in period

a
Each period in the periodic table indicates the value of n for the outermost or the valence shell.
hs
The total number of elements in each period is twice the number of orbitals available in the
energy level that is being filled.
at
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(1) The first period corresponds to the filling of electrons in the first energy shell i.e. (k
shell),n=1.Since this energy shell has only 1 orbital i.e. 1s which can accommodate only 2
ita

electrons, therefore, first period has only 2 elements.

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(2) The second period corresponds to the filling of electrons in the second energy shell (L shell)
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i.e. n=2.This shell has 4 orbitals( one 2s and three 2p) which can accommodate 8 electrons,
therefore second period contains 8 electron. It starts with Lithium (Z=3) and ends at neon (Z=
w

10).
w

(3) The third period corresponds to the filling of electron in the third shells, i.e. n=3.This shell has
(w

9 orbitals ( one 3s, three 3p and five 3d) .3d orbital have even higher energy than 4s orbital.
Therefore 3d orbitals are filled only after filling of 4s orbital. Third period involves the filling of
only 4 orbitals( one 3s and three 3p) and thus contains 8 elements. It starts with sodium(Z=11)
and ends at argon (Z= 18).

(4) The Fourth period corresponds to the filling of electrons in the fourth energy level, n=4. It
starts with potassium( Z=19) and ends at calcium (Z= 20).

After the filling of 4s orbitals, the filling of five 3d orbitals begins since the energy of 3d orbital is
lower than those of 4p orbitals but higher than that of 4s orbital. The filling of 4d and 4f orbital
does not occur in this period since their energies are higher than that of even 5s orbital. The
filling of the 3d orbital starts from scandium( Z= 21) and ends at Zinc( Z= 30).These 10 elements

(12)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

constitute the 3d transition series.

The filling of 4p orbital begins at gallium( Z=31)and ends at krypton( Z=36) which has the outer
electronic configuration as 4s2 3d10 4p6 .In the 4th period, the filling of only 9 orbitals( one 4s,
five 3d and three 4p ) occurs which can accommodate at the maximum 18 electrons. Therefore
4th period contain 18 electrons from potassium to Krypton.

(5) The fifth period also contains 18 elements since only 9 orbitals ( one 5s, five 4d and three 5p)
are available for filling with electrons. It begins with rubidium(Z= 37) in which one electron
enters 5s orbital. After the filling of 5s orbital, the filling of 4d orbital starts at yittrium (Z=39) and
ends at cadmium (Z= 48).These ten elements constitute 4d transition series. Filling of 5p orbitals

)
starts at indium (Z= 49) and ends at xenon ( Z=54).

m
(6) The sixth period corresponds to the filling of 6th energy level i.e. n= 6.Only 16 orbitals( one

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5s, five 4d and three 5p) are available for filling with electrons, therefore 6th period contains 32
elements. It begins with caesium(Z=55) in which one electron enters the 6s orbital and ends up

la
with radon(Z=86) in which the filling of 6p orbital is complete. After the filling of 6s Orbital, the

a
next electron enters the 5d orbital and therefore the filling of seven 4f orbitals begins with
hs
Cerium(Z=58) and ends up with lutetium(Z=71).These 14 elements constitutes the first inner
transition series called lanthanides or lanthanoids.
at
Filling of 5d orbitals which started at lanthanum continuous from hafnium( Z=72) till it is filled at
lp

mercury(Z=80). These 10 elements constitutes the 5d- transition series. After the filling of 5d
ita

orbitals, the filling of 6p orbitals starts at thallium(Z=81) and ends at the radon (Z=86).
ig

(7) The seventh period corresponds to filling of 7th energy shells i.e. n=7. It also contain 32
elements corresponds to the filling of 16 orbitals(one 7s, seven 5f, five 6d and three 7p ).
.d
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After the filling of 7s orbital, the next two electrons enters the 6d orbitals and therefore the
filling of seven 5f orbitals begin with proactinium(Z=91) and ends up with lawrencium(Z=103).
w
(w

Thorium does not have any electron in the 5f orbital, yet get it is considered to be a f block
element since its properties resemble more the f block element than the d block elements.
These 14 elements from thorium(Z=90) to lawrencium(Z=103) constitute the second (or 5f) inner
transition series which is called as actinides are actinoids.

Filling of 5d orbitals which started at actinum(Z=89) continues till it is completed at these

Uub(Z=112).These 10 elements constitute the 6d transition series. The filling of 6d, orbital the
filling of 7p orbitals begins at Uut (Z= 118) which ends at Uut (Z=118) which belongs to noble gas
family.

The first three periods containing 2,8,8 elements and are known as short periods while the next
three periods containing 18 ,18, 32 elements are called Long periods

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

Group wise electronic configuration

The elements in the same group or vertical column have similar valence shell electron electronic
configuration i.e. they have the same number of electrons in the outer orbitals and hence have
similar properties. Elements of group 1 all have ns1 valence shell electronic configuration.
Elements of group 17 all have ns2 np5 valence shell electronic configuration.

Prediction of period, group and block of a given element

The period of an element corresponds to the principal quantum number of the valence shell.

)
The block of an element corresponds to the type of orbital which receive the last electron.

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The group of an element is predicted from the number of electrons in the valence shell or/and

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penultimate shell as follows:

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a)For s block elements ,group number is equal to the number of valence electrons.

a
b) For p block elements ,group number is equal to 10+number of electrons in the valence shell.
hs
c)For d block elements ,group number is equal to the number of electrons in a (n-1) sub shell +
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the number of electrons in valence shell.
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Question :Write the electronic configuration of the element with atomic number 29. Predict the
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period, group number and block to which it belongs.

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Answer : Z = 29 1s2 2s2 2p6 3s2 3p6 3d10 4s1

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Elements receive the last electron in the 3d orbital ,therefore, it belongs to d block elements and
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its group number = No. of electrons in the penultimate shell and valence shell = 10+ 1 =11
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The period of the element = No. of principal quantum number of the valence shell = 4th
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Summary-
1. Periodic table: Arrangement of elements in the increasing order of atomic number such
that elements with similar properties fall under same vertical column.
2. Group: A vertical column of elements in the periodic table.
3. Period: A horizontal row of elements in the periodic table.
4. Long form of periodic table has 18 groups and 7 periods. Sixth period is the longest and
first period is the smallest.
5. s-Block elements: Elements of groups 1 and 2. Their general valence shell electronic
configuration is ns1–2.

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

6. p-Block elements: Elements of groups 13, 14, 15, 16, 17 and 18. Their general valence shell
electronic configuration is ns2np1–6.
7. d-Block elements: Elements of groups 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12. Also known as
transition elements. Their general valence shell electronic configuration is (n–1)d1–10 ns1–2.
10 0
46Pd is exception (4d 5s ).

8. f-Block elements: The two horizontal rows of elements at the bottom of the table. Also
known as inner transition elements. Their general valence shell electronic configuration is
(n–2)f1–14 (n–1)d0–1 ns2.
9. Covalent radius: Half of the internuclear distance between two atoms of the element held

)
by a single covalent bond.

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10. Van der Waal’s radius: Half of the internuclear distance between two nearest atoms

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belonging to two adjacent molecules in solid state.
11. Metallic radius: Half of the internuclear distance between two nearest atoms in the metallic

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lattice.

a
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12. Isoelectronic ions: The ions having same number of electrons but different nuclear charge.
Example: (i) N3–, O2–, F–, Na+, Mg2+, Al3+; (ii) P3–, S2–, Cl–, K+, Ca2+, Sc3+
at
13. Among isoelectric ions, greater the nuclear charge smaller is the size.
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14. Ionization enthalpy: The minimum amount energy required to remove the outermost
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electron from an isolated gaseous atom of the element.

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15. Ionization enthalpy increases along the period and decreases down the group.
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16. Be, Mg, N, P and noble gases have exceptionally high values of ionization enthalpies due to
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their stable electronic configurations.

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17. Electron gain enthalpy: The enthalpy change taking place when an electron is added to an
isolated gaseous atom of the element.
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18. Electron gain enthalpy becomes more negative as we move along the period and becomes
less negative down the group.
19. Successive electron gain enthalpies are always positive.
20. Helium has the highest value of ionization enthalpy in periodic table.
21. Chlorine has the highest negative electron gain enthalpy in periodic table.
22. Electronegativity: It is the tendency of an atom in a molecule to attract towards itself the
shared pair of electrons.
23. Fluorine is the most electronegative element whereas Caesium is the least electronegative
element in periodic table.

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

24. Unlike ionisation energy and electron affinity, electronegativity is the property of atom of
an element in combined state.
25. Electropositive or metallic character is related to the ionisation energy of the element. The
elements having low I.E. are more electropositive or more metallic in character.
26. Valence of an element belonging to s or p-block is either equal to the number of valence
electrons or eight minus the number of valence electron.
27. The chemical reactivity is maximum at the two extreme ends of the periodic table and is
least in the centre.
28. Among alkali metals reactivity increases on descending the group while among halogens the

)
reactivity decreases on descending the group.

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29. The basic character of oxides decreases while the acidic character increases on going from

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left to right in a period.

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30. Oxides of metals are generally basic while that of non-metals are acidic in nature.

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31. The similarity between a pair of elements in period second and third located diagonally in
hs
the periodic table is called the diagonal relationship.
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(16)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

Important Questions
Multiple Choice questions-
Question 1. The group number, number of valence electrons, and valency of an element with
the atomic number 15, respectively, are:
(a) 16, 5 and 2
(b) 15, 5 and 3
(c) 16, 6 and 3
(d) 15, 6 and 2

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Question 2. The d-block elements consist mostly of

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(a) Monovalent metals
(b) All non-metals

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(c) Elements which generally form stoichiometric metal oxide

a
(d) Many metals with catalytic properties hs
Question 3. Which of the following has the highest boiling point?
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(a) Ne
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(b) Xe
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(c) Ar
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(d) Kr.
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Question 4. The chemistry of lithium is very similar to that of magnesium even though they
are placed in different groups. Its reason is:
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(a) Both are found together in nature

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(b) Both have nearly the same size

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(c) Both have similar electronic configuration

(d) The ratio of their charge and size (i.e. charge density) is nearly the same
Question 5. Which one of the following groupings represents a collection of isoelectronic
species? (At. nos: Cs-55, Br-35)
(a) Na+, Ca2+, Mg2+
(b) N3-, F–, Na+
(c) Be, Al3+, Cl–
(d) Ca2+, Cs+, Br
Question 6. Which of the following has the maximum number of unpaired electrons?

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

(a) Mg2+
(b) Ti3+
(c) V3+
(d) Fe2+
Question 7. In the periodic table, the element with atomic number 16 will be placed in the
group
(a) Third
(b) Fourth

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(c) Fifth

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(d) Sixth

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Question 8. Representative elements are those which belong to
(a) p and d – Block

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(b) s and d – Block
(c) s and p – Block
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(d) s and f – Block
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Question 9. Which pair of elements belongs to same group?

(a) Elements with atomic no. 17 and 38
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(b) Elements with atomic no. 20 and 40

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(c) Elements with atomic no. 17 and 53

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(d) Elements with atomic no. 11 and 33

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Question 10. The most electronegative element of the periodic table is

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(a) Iodine
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(b) Sulphur
(c) Oxygen
(d) Fluorine.
Question 11. In the third period of the Periodic Table the element having smallest size is
(a) Na
(b) Ar
(c) Cl
(d) Si
Question 12. The element with highest second ionization energy is

(19)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

(a) Cl
(b) S
(c) Na
(d) Mg
Question 13. Which of the following properties generally decreases along a period?
(a) Ionization Energy
(b) Metallic Character
(c) Electron Affinity

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(d) Valency.

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Question 14. Increasing order of electronegativity is

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(a) Bi < P < S < Cl

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(b) P < Bi < S < Cl

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(c) S < Bi < P < Cl
(d) Cl < S < Bi < P
hs
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Question 15. Which of the following oxides is amphoteric in character?
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(a) SnO2
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(b) CO2
(c) SiO2
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(d) CaO
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Very Short:
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1. An element is present in the third period of the p-block. It has 5 electrons in its
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outermost shell. Predict its group. How many unpaired electrons does it have?
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2. An element X with Z = 112 has been recently discovered. Predict its electronic
configuration and suggest the group in which it is present.
3. The electronic configuration of an element is 1s2 2s2 2p6 3s2 3p5. Name the period and
the group to which it belongs?
4. Arrange Cl, Cl–, Cl+ ion in order of increasing size.
5. Arrange the following in increasing order of size.
N3-, Na+, F–, O2-, Mg2+
6. Give the formula of one species positively charged and one negatively charged that will
be isoelectronic with Ne.
7. Argon has atomic number 18 and belongs to the 3rd period and 18th group. Predict the
(20)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

group and period for the element having atomic number 19.
Short Questions:
1. Do elements with high I.E. have high E.A.?
2. What is a periodic classification of elements?
3. Distinguish between s and p block elements.
4. Explain why ionization enthalpies decrease down a group of the Periodic Table.
5. Why does the first ionization enthalpy increase as we go . from left to right across a
given period of the Periodic Table.

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6. How do atomic radii vary across a period with an atomic number in the periodic table?

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Long Questions:

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1. Electronic configuration of the four elements are given below: Arrange these elements in

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increasing order of their metallic character. Give reasons for your answer.

a
(i) [Ar]4s2
(ii) (ii) [Ar]3d10 4s2
hs
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(iii) [Ar]3d10 4s2 4p6 5s2
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(iv) [Arl 3d10 4s2 4p6 5s1

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2. Explain the important general characteristics of groups in the modem periodic table in
brief.
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3. Explain the electronic configuration in periods in the periodic table. „

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4. Explain the variation of valence in the periodic table.

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Assertion Reason Questions:

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1. In the following questions, a statement of Assertion (A) followed by a statement of

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Reason (R) is given. Choose the correct option out of the choices given below each
question.
Assertion (A) : Generally, ionisation enthalpy increases from left to right in a
period.
Reason (R) : When successive electrons are added to the orbitals in the
same principal quantum level, the shielding effect of inner
core of electrons does not increase very much to compensate
for the increased attraction of the electron to the nucleus.
(i) Assertion is correct statement and reason is wrong statement.

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

(ii) Assertion and reason both are correct statements and reason is correct
explanation of assertion.
(iii) Assertion and reason both are wrong statements.
(iv) Assertion is wrong statement and reason is correct statement.
2. In the following questions, a statement of Assertion (A) followed by a statement of
Reason (R) is given. Choose the correct option out of the choices given below each
question.
Assertion (A) : Boron has a smaller first ionisation enthalpy than beryllium.
Reason (R) : The penetration of a 2s electron to the nucleus is more than

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the 2p electron hence 2p electron is more shielded by the

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inner core of electrons than the 2s electrons.
(i) Assertion and reason both are correct statements but reason is not

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correct explanation for assertion.

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(ii) Assertion is correct statement but reason is wrong statement.
(iii) Assertion and reason both are correct statements and reason is correct
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explanation for assertion.
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(iv) Assertion and reason both are wrong statements.

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Case Study Based Question:

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1. Comprehension given below is followed by some multiple choice questions. Each

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question has one correct option. Choose the correct option. In the modern periodic table,
elements are arranged in order of increasing atomic numbers which is related to the
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electronic configuration. Depending upon the type of orbitals receiving the last electron,
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the elements in the periodic table have been divided into four blocks, viz, s, p, d and f.
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The modern periodic table consists of 7 periods and 18 groups. Each period begins with
the filling of a new energy shell. In accordance with the Arfbau principle, the seven
periods (1 to 7) have 2, 8, 8, 18, 18, 32 and 32 elements respectively. The seventh period
is still incomplete. To avoid the periodic table being too long, the two series of f-block
elements, called lanthanoids and actinoids are placed at the bottom of the main body of
the periodic table.
(1) The element with atomic number 57 belongs to
(a) s-block
(b) p-block
(c) d-block
(d) f-block
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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

(2) The last element of the p-block in 6th period is represented by the outermost
electronic configuration.
(a) 7s2 7p6
(b) 5f14 6d10 7s2 7p0
(c) 4f14 5d10 6s2 6p6
(d) 4f14 5d10 6s2 6p4
(3) Which of the elements whose atomic numbers are given below, cannot be
accommodated in the present set up of the long form of the periodic table?
(a) 107

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(b) 118

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(c) 126
(d) 102

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(4) The electronic configuration of the element which is just above the element with

a
atomic number 43 in the same group is ________.
hs
(a) 1s2 2s2 2p6 3s2 3p6 3d5 4s2
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(b) 1s2 2s2 2p6 3s2 3p6 3d5 4s3 4p6
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(c) 1s2 2s2 2p6 3s2 3p6 3d6 4s2

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(d) 1s2 2s2 2p6 3s2 3p6 3d7 4s2

(5) The elements with atomic numbers 35, 53 and 85 are all ________.
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(a) Noble gases

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(b) Halogens
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(c) Heavy metals

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(d) Light metals

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2. Read the passage given below and answer the following questions:
When an electron is added to a gaseous atom in its ground state to convert it into a
negative ion, the enthalpy change accompanying the process is called the electron gain
enthalpy (∆eg H). It is a direct measure of the ease with which an atom attracts an
electron to form anion.

The most stable state of an atom is the ground state. If an isolated gaseous atom is in
excited state, comparatively lesser energy will be released on adding an electron. So,
electron gain enthalpies of gaseous atoms must be determined in their ground states.
Therefore, the terms ground state and isolated gaseous atom has been also included in
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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

the definition of electron gain enthalpy. Like ionisation enthalpy, electron gain enthalpy is
measure either in electron volts per atom or kJ per mole.
(1) Noble gases have positive electron gain enthalpy due to:
(a) Stable configuration
(b) Large size
(c) High reactivity
(d) Unstable configuration
(2) The electron gain enthalpy of O or F is less than that of S or Cl. It is due to:

)
(a) Small size

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(b) Less repulsion

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(c) Large size
(d) High electronegativity

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(3) The electron gain enthalpy (in kJ/mol) of fluorine, chlorine, bromine and iodine,
respectively, are: hs
(a) -333, -325, -349 and -296
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(b) -296, -325, -333 and -349
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(c) -333, -349, -325 and -296

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(d) -349, -333, -325 and -296

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(4) Why beryllium has higher ionization enthalpy than boron?

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(a) More penetration of s-electron

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(b) More penetration of p-electron

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(c) Large size

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(d) Small size

Answer Key:
MCQ
1. (a) 15, 5 and 3
2. (d) Many metals with catalytic properties
3. (b) Xe
4. (d) The ratio of their charge and size (i.e. charge density) is nearly the same
5. (b) N3-, F–, Na+
6. (d) Fe2+
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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

7. (d) Sixth
8. (c) s and p – Block
9. (c) Elements with atomic no. 17 and 53
10.(d) Fluorine.
11.(b) Ar
12.(c) Na
13.(b) Metallic Character
14.(a) Bi < P < S < Cl

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15.(a) SnO2

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Very Short Answer:

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1. It belongs to the 15th group (P). It has 3 unpaired electrons.

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2. Rn] 5f14 6d10 7s2. It belongs to the 12th group.

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3. Third-period Group 17. hs
4. CP < Cl < CP.
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5. Mg2 + < Na+< F– < O2- < N3-
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6. Na+, F–.
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7. Group I, Period 4th.

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Short Answer:
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Ans: 1. Normally is true that the elements with haying high value of I.E. have a high value of E
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affinity. But however, there are marked exceptions. It is seen that elements, with stable
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electronic configurations, have very high values of I-Energies as it is difficult to remove

electrons as is the case with 15th and 18th group elements but in such case, electron cannot
be added easily so that is why elements of 15th group have almost zero E.A. and elements of
18th group have got zero E.A. whereas their Ionization energy values are very high.
Ans: 2. By periodic classification of the elements we mean the arrangement of the elements
in such a way that the elements with similar physical and chemical properties are grouped
together and for this various scientists made contributions but however the contributions
made by Mendeleev are of great significance and he gave a periodic table which called as
Mendeleev’s Periodic ‘Table which was older and replaced by the long form of the periodic
table.
Ans: 3. They can be distinguished as follows: s block elements:

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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

1. They have got the general configuration of the valence shell, ns1-2.
2. They are all metals.
3. Their compounds are mostly ionic.
4. They are generally strong reducing agents.
5. They mostly impart characteristic color to the flame.
6. They have low ionization energies.
7. They show fixed oxidation states,

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p block elements:

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1. The valence shell electronic configuration of p block elements in ns2 p1-6.

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2. They are mostly non-metals.
3. Their compounds are mostly covalent.
hs
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4. They are generally strong oxidizing agents.
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5. Mostly they do not impart color to the flame.

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6. They have got a comparatively higher value of I.E.

7. They show variable oxidation states.,
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Ans: 4. The decrease in ionization enthalpies down any group is because of the following
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factors:
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1. There is an increase in the number of the main energy shells

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2. moving from one element to another.

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3. There is also an increase in the magnitude of the screening effect due to the
gradual increase in the number of inner electrons.
Ans: 5. The value of ionization enthalpy increases with the increase in atomic number across
the period.
This is due to the fact that in moving across the period from left to right.,
1. Nuclear charge increases regularly by one unit.
2. The progressive addition of electrons occurs at the same level.
3. Atomic size decreases.
This is due to the gradual increase in nuclear charge and a simultaneous decrease in atomic
size the electrons are more and more tightly bound to the nucleus. This results in a gradual
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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

increase in ionization energy across the period.

Ans: 6. Variation of Atomic radii across a period: atomic radii decrease with the increase in
the atomic number in a period. For example, atomic radii decrease from lithium to fluorine in
the second period.
In moving from left to right across the period, the nuclear charge increases progressively by
one unit but the additional electron goes” to the same principal shell. As a result, the
electron cloud is pulled closer to the nucleus by increased effective nuclear charge. This
causes a decrease in atomic size.

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hs
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Variation of the atomic radius with an atomic number across the second period
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Long Answer:
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Ans: 1. (i) [Ar]4s2 is Calcium metal with At. no. = 20.

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(ii) [Ar]3d10 4s2 is Zinc metal with At. no. = 30.

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(iii) [Ar]3d10 4s2 4p6 5s2 is Strontium metal with At. no. = 38.
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(iv) [Ar] 3d10 4s2 4p6, 5s1 is*Rubidium metal with At. no. = 37.
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Alkali metals are the most metallic, followed by alkaline earth metals and transition metals.
Among alkali metals – Rubidium (37) is the most metallic. Among alkaline earth metals (Ca,
Sr) Sr (Strontium) is more metallic than Calcium (Ca) as the metallic character increases from
top to bottom in a group. Zinc – the transition metal is the least metallic. Thus metallic
character increases from
Zn < Ca < Sr < Rb or (ii) < (i) < (iii) < (iv)
Ans: 2. The elements of a group show the following important similar characteristics.
(0 Electronic configuration. All elements in a particular group have similar outer electronic
configuration e.g., all elements of group I’, i.e., alkali metals have ns1 configuration in
their valency shell. Similarly, group 2 elements (alkaline Earths) Haye ns2 outer
configuration and halogens (group 17) have ns2 np5 configuration (where n is the

(27)
 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

outermost shell).
(it) Valency. The valency of an element depends upon the number of electrons in the
outermost shell. So elements of a group show the same valency, e.g., elements of group 1
show + 1 valency and group 2 show + 2 valencies i.e. valency i.e., NaCl > MgCl2 etc.
(iii) Chemical properties. The chemical properties of the elements are related to the number
of electrons in the outermost shell of their atoms. Hence all elements belonging to the
same group show similar chemical properties. But the degree of reactivity varies gradually
from top to bottom in a group. For example, in group 1 all the elements are highly
reactive metals but the degree of reactivity increases from Li to Cs. Similarly, elements of
group 17, i.e., halogens: F, Cl, Br, I are all non-metals and they’re- reactivity goes on

)
decreasing from top to bottom.

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Ans: 3. Each successive period in the periodic table is associated with the filling Up of the

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next higher principal energy level (n – 1, n – 2, etc.). It can be readily seen that the
number of elements in each period is twice the number of atomic orbitals available in the

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energy level that is being filled. The first period starts with the filling of the lowest level

a
(1s) and has thus the two elements – hydrogen (1s1) and helium (1s2) when the first shell
hs
(K) is completed. The second period starts with lithium and the third electron enters the
2s orbital.
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The next element, beryllium has four electrons and has the electronic configuration 1s2 2s2.
lp

Starting from the next element boron, the 2p orbitals are filled with electrons when the L
shell is completed’ at neon (2s2 2p6). Thus there are 8 elements in the second period. The
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third period (n = 3) being at sodium, and the added electron enters a 3s orbital.
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Successive filling of 3s and 3p orbitals give rise to the third period of 8 elements from
sodium to argon.
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The fourth period (n = 4) starts at potassium with the filling up of 4p of 4s orbital. Before the
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4p orbital is filled, the filling up of 3d orbitals becomes energetically favorable and we

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come across the so-called 3d transition series of elements. The fourth period ends at
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krypton with the filling up of the 4p orbitals. Altogether we have 18 elements in the
fourth period. The fifth period (n = 5) beginning with rubidium is similar to the fourth
period and contains the 4d transition series starting at yttrium (Z = 39).
This period ends at xenon with the filling up of the 5p orbitals. The sixth period (n = 6)
contains 32 elements and successive electrons enter 6s, 4/, 5d, and 6p orbitals, in that
order. Filling up of the 4/ orbitals being with cerium, (Z = 58) and ends at lutetium (Z = 71)
to give the 4/-inner transition series which is called the lanthanide series. The seventh
period (n = 7) is similar to the sixth period with the successive filling up of the 7s, 5f, 6d,
and 7p orbitals and includes most of the man-made radioactive elements.
This period will end at the element with atomic number 118 which would belong to the
noble gas family. Filling up of the 5f orbitals after actinium (Z = 89) gives the 5f-inner
transition series known as the actinide series. The 4f and 5f transition series of elements
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 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES
03

are placed separately in the periodic table to maintain its structure and to preserve the
principle of classification by keeping elements with similar properties in a single column.
Ans: 4. Variation of valence in a group as well as across a period in the periodic table occurs
as follows:
1. In a group: All elements in a group show the same valency. For example, all alkali metals
(group 1) show a valency of 1+. Alkaline earth metals (group 2) show a valency of 2+.
However, the heavier elements of p-block elements (except noble gases) show two valences:
one equal to the number of valence electrons or 8-No. of valence electron# and the other
two less. For example, thallium (Tl) belongs to group 13. It shows valence of 3+ and 1+.

)
Lead (Pb) belongs to group 14. If shows valance of 4+ and 2+.

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Antimony (Sb) and Bismuth (Bi) belong to group 15. They show valence of 5+ and 3+ being

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more stable.
This happens due to the non-participation of tie two s-electrons present in the valence shell

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of these elements. This non-participation of one pair of s-electrons in bonding is called

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the inert-pair effect.
hs
3. In a period: The number of the valence electrons increases – in going from left to right
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in a period of the periodic table. Therefore, the valency of the elements in a period
first increases, and then decreases.
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Assertion Reason Answer:

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1. (ii) Assertion and reason both are correct statements and reason is correct.
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2. (iii) Assertion and reason both are correct statements and reason is correct.
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Case Study Answer:

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1. Answer:
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(1) (c) d-block

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(2) (c) 4f14 5d10 6s2 6p6

(3) (c) 126
(4) (a) 1s2 2s2 2p6 3s2 3p6 3d5 4s2
(5) (b) Halogens
2. Answer:
(1) (a) Stable configuration
(2) (a) Small size
(3) (c) -333, -349, -325 and -296
(4) (a) More penetration of s-electron

(29)
 CHEMISTRY

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CHAPTER 4: CHEMICAL BONDING AND MOLECULAR STRUCTURE

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

CHEMICAL BONDING AND

MOLECULAR STRUCTURE

Introduction:

Structure and Bonding is the heart of chemistry. Chemical bond is very important to explain the
properties and structure of compound. The important aspect of each type of force is its relative
strength, how rapidly it decreases with increasing distance and whether it is directional in nature
or not.

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Chemical Bond:

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It is the force of attraction between two atoms which hold them together in a compound or
molecule. Nature loves stability and bond formation is associated with stability. Every element

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has a tendency to occupy inert electronic configuration which is considered as very stable.
Noble gas electronic configuration can be achieved by

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1. Transference of electrons
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2. Mutual sharing of electrons
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3. Donation of lone pair of electrons

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Types of Bond
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In order to explain the formation of a chemical bond in terms of electrons, Lewis postulated that
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atoms achieve stable octet when they are linked by a chemical bond. On the basis of this
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chemical bonds are following type:

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1. Ionic bond
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2. Covalent bond
3. Co-ordinate bond
4. Metallic bond
5. Hydrogen bond
6. van der Waal’s bond

Lewis Dot Structures

Valence Electrons: In the formation of a molecule only the outer shell electrons take part in
chemical bond combination and they are known as valence electrons. In Lewis symbols, an
element is shown with symbol and valence electrons.

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04

Octet Rule
It is proposed by Kossel and Lewis and according to this, "Every atom has a tendency to attain
Noble gas electronic configuration or to have 8 valence electrons". This is known as law of octet
rule or if it has two valence electrons then this is known as law of duplet. According to Lewis,
only those compounds will be stable which follow octet rule.

Formal Charge
Formal charge on an atom is the difference between the number of valence electrons is an
isolated atom and the number of electrons assigned to that atom in a Lewis structure. It is
expressed as:

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hs
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Ionic Bond
An ionic bond is formed by complete transference of one or more electrons from the valence
shell of one atom to the valence shell of another atom. In this way both the atoms acquire stable
electronic configurations of noble gases. The atom which loses electron becomes a positive ion
and the atom which gains electron becomes negative ion.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

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Note: Electrovalency is the number of electrons lost or gained during the formation of an ionic
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bond or electrovalent bond.

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Characteristics of Ionic Compounds:

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1. They are hard, brittle and crystalline.

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2. They have high melting and boiling points.

3. They are polar in nature.
4. The linkage between oppositely charged ions is non rigid and non directional.
5. They are soluble in polar solvents such as water and insoluble in non polar solvents such as
CCl4, Benzene, ether etc.
6. They are good conductors of electricity in fused state and in solution due to mobility of the
ions. They are bad conductors of electricity in solid state because ions are unable to move.

Covalent Bond

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

A force which binds atoms of same or different elements by mutual sharing of electrons is called
a covalent bond. If the combining atoms are same the covalent molecule is known as
homoatomic. If they are different, they are known as heteroatomic molecule.

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hs
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Valence Bond Theory (VBT)

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Valence bond theory was introduced by Heitler and London (1927) and developed by Pauling and
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others. It is based on the concept of atomic orbitals and the electronic configuration of the
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atoms. Let two hydrogen atoms A and B having their nuclei NA and NB and electrons present in
them are eA and eB. As these two atoms come closer new attractive and repulsive forces begin
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to operate.

1. The nucleus of one atom is attracted towards its own electron and the electron of the
other and vice versa.
2. Repulsive forces arise between the electrons of two atoms and nuclei of two atoms.
Attractive forces tend to bring the two atoms closer whereas repulsive forces tend to push
them apart.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

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Orbital overlap concept

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If we refer to the minimum energy state in the formation of hydrogen molecule the two H-

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atoms are enough near so as to allow their atomic orbitals to undergo partial interpenetration.
This partial interpenetration of atomic orbitals is called overlapping of atomic orbitals. The

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overlap between the atomic orbitals can be positive, negative or zero depending upon the

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characteristics of the orbitals participating to overlap.
hs
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lp
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Types of overlapping
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The covalent bonds can be classified into two different categories depending upon the type of
overlapping. These are:
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Sigma (σ) bond: This type of covalent bond is formed by the axial overlapping of half-filled
atomic orbitals. The atomic orbitals overlap along the internuclear axis and involve end to end
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or head on overlap. There can be three type of axial overlap among s and p-orbitals as
discussed below:

i. s-s overlap: In this case, there is overlap of two half-filled s-orbitals along the internuclear
axis as shown below.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

ii. s-p overlapping: It involves the overlapping of half filled s-orbitals of one atom with the half
filled p-orbitals of the other atom. The bond thus formed is called s-p sigma bond.

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hs
p-p overlapping: It involves the co-axial overlapping between half filled p-orbitals of one
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iii.
atom with half filled p-orbitals of the other atom. The bond as formed is called p-p sigma
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bond.
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ig
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pi (π) bond: This type of covalent bond is formed when the atomic orbitals overlap in such a
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way that their axis remain parallel to each other and perpendicular to the internuclear axis. The
orbitals formed due to sidewise overlapping consists of two saucer type charged clouds above
and below the plane of the participating atoms. The electrons involved in the π bond formation
are called pi-electrons.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

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Hybridisation: Hybridisation is the process of intermixing of the orbitals of slightly different

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energies so as to redistribute their energies, resulting in the formation of new set of orbitals of
equivalent energies and shape. The atomic orbitals combine to form new set of equivalent
orbitals known as hybrid orbitals.

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Salient Features of Hybridisation: hs
i. The number of hybrid orbitals is equal to the number of the atomic orbitals that get
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hybridised.
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ii. The hybridised orbitals are always equivalent in energy and shape.
iii. The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
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iv. The type of hybridisation indicates the geometry of the molecules.

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Important conditions for hybridisation:

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i. The orbitals present in the valence shell of the atom are hybridised.
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ii. The orbitals taking part in hybridisation must have only a small difference of energies.
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iii. Promotion of electron is not essential condition prior to hybridisation.

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iv. It is not necessary that only half filled orbitals participate in hybridisation.

Types of hybridisation
There are many different types of hybridisation depending upon the type of orbitals involved in
mixing such as sp3, sp2, sp, sp3d, sp3d2 etc.

i. sp-hybridisation: In this hybridisation one s and one p orbitals hybridise to produce two
equivalent hybrid orbitals, known as sp hybrid orbitals. The two sp-hybrid orbitals are
oriented in a straight line making an angle of 180° and therefore the molecule possesses
linear geometry. Each of hybrid orbitals has 50% s-character and 50% p-character.

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Example of molecules having sp-hybridisation are BeF2, BeCl2, BeH2 etc.

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a la
hs
sp2-hybridisation: In this hybridisation one s and one 2p orbitals hybridise to produce three
at
ii.
equivalent hybrid orbitals, known as sp2 hybrid orbitals. sp2 hybrid orbitals are larger in size
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than sp-hybrid orbitals but slightly smaller than that of sp3 hybrid orbitals. Each sp2 hybrid
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orbitals has 1/3 (or 33.33%) s-character and 2/3 (or 66.7%) p-character. Example, BF3, BCl3,
BH3 etc.
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w
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iii. sp3d-hybridisation: This type of hybridisation involves mixing of one s, three p and one d-
orbitals to form five sp3d hybridised orbitals which adopt trigonal bipyramidal.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

Formation of PCl5: The ground state electronic configuration of phosphorus is 1s2 2s2 2p6 3s2
3p3. Under the conditions of bond formation the 3s-electrons get unpaired and one of the
electron is promoted to vacant 3dz2 orbital. The ground state and excited state
configurations of phosphorus are shown below:

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hs
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iv. sp3d2-hybridisation: In this type of hybridisation one s, three p and two d-orbitals undergo
intermixing to form six identical sp3d2 hybrid orbitals. These six orbitals are directed towards
the corners of an octahedron and lie in space at an angle of 90° to one another.
The ground state outer configuration of 16S is 3s2 3p4. In the excited state the electron pairs

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

in 3s and 3px orbitals get unpaired and one out of each pair is promoted to vacant 3dz2 and
3dx2-y2 orbitals. The ground state and excited state configuration of 16S are given as follows:

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hs
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Valence Shell Electron Pair Repulsion (VSEPR) Theory

Sidgwick and Powell in 1940, proposed a simple theory based on repulsive character of electron
pairs in the valence shell of the atoms. It was further developed by Nyholm and Gillespie
(1957). Main Postulates are the following:
i. The exact shape of molecule depends upon the number of electron pairs (bonded or non
bonded) around the central atoms.
ii. The electron pairs have a tendency to repel each other since they exist around the central

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

atom and the electron clouds are negatively charged.

iii. Electron pairs try to take such position which can minimize the rupulsion between them.
iv. The valence shell is taken as a sphere with the electron pairs placed at maximum distance.
v. A multiple bond is treated as if it is a single electron pair and the electron pairs which
constitute the bond as single pairs.

Bond Parameters:
i. Bond Angle: It is the distance between two consecutive crests or troughs and is denoted by
λ. It is defined as the angle between the orbitals containing bonding electron pairs around

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the central atom in a molecule/complex ion. Bond angle is expressed in degree which can be

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experimentally determined by spectroscopic methods.

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ii. Bond Length: Bond length is defined as the equilibrium distance between the nuclei of two
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bonded atoms in a molecule.

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iii. 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.

iv. Bond Order: Bond order is defined as half of the difference between the number of

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

electrons present in bonding and antibonding molecular orbitals. The bond order may be a
whole number, a fraction or even zero. It may also be positive or negative.
𝟏
Bond order (B.O.) = [𝐍𝐛 − 𝐍𝐚]
𝟐

v. Bond Enthalpy: It is defined as the amount of energy required to break one mole of bonds
of a particular type between two atoms in a gaseous state. The unit of bond enthalpy is kJ
mol–1. For example, the H – H bond enthalpy in hydrogen molecule is 435.8 kJ mol–1.

Molecular Orbital Theory (MOT)

Molecular orbital (MO) theory was developed by F. Hund and R.S. Mulliken in 1932. According

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to MOT, a molecule is considered to be quite different from the constituent atoms. All the
electrons belonging to the atoms constituting a molecule are considered to be moving along

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the entire molecule under the influence of all the nuclei. Thus, a molecule is supposed to have
orbitals of varying energy levels, in same way as an atom. These orbitals are called molecular

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orbitals.

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Energy Level Diagram for Molecular Orbitals: hs
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Resonance
When light of a suitable frequency is allowed to incident on a metal, ejection of electrons take
place. This phenomenon is known as photo electric effect.
When a compound has same molecular formula but different structural formulas and
structures differ with respect to electrons only. These structures are known as resonating
structures or canonical structures. None of these structures can explain all the properties of
that compound. This phenomenon is known as resonance.

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Hydrogen Bonding
When highly electronegative elements like nitrogen, oxygen, flourine are attached to hydrogen
to form covalent bond, the electrons of the covalent bond are shifted towards the more
electronegative atom. Thus, partial positive charge develops on hydrogen atom which forms a
bond with the other electronegative atom. This bond is known as hydrogen bond and it is

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weaker than the covalent bond.

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Types of Hydrogen Bonding:
i. There are two types of hydrogen bonding: It is a type of hydrogen bonding between two

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similar or dissimilar molecules. Example : H – F, HF and water, NH3, NH3 and water, alcohol,

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alcohol and water etc.
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ii. Intramolecular hydrogen bonding: It is a type of hydrogen bonding within the molecule.
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Example : Salicylaldehyde, O-nitrophenol etc.

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Applications of Hydrogen Bonding

i. State: Hydrogen bonding may affect the state of a compound. For example, H 2O is liquid at
room temperature whereas H2S is gas. It is due to presence of intermolecular hydrogen
bonding between H2O molecules, which is not present in H2S molecules.
ii. Solubility: Only those covalent molecules are soluble in water which have tendency to form

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

intermolecular hydrogen bonding with water molecules.

iii. Boiling point: Intermolecular hydrogen bonding increases the boiling point of compound.
For example, NH3 has higher boiling point than PH3. This is because, there is intermolecular
hydrogen bonding in NH3 but not in PH3.
iv. Density of ice is lower than water: In ice, hydrogen bonding gives rise to a cage like
structure of H–O–H molecules, in which each H–O–H molecule is linked tetrahedrally to four
other H–O–H molecule. In this structure, some vacant spaces are formed, which decrease
the density of ice.

Metallic Bonding

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The force that binds a metal atom to a number of electrons within its sphere of influence is
known as metallic bond.

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This model could easily explain the following properties of metals:

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i. High electrical conductivity

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ii. High thermal conductivity
iii.
iv.
Bright metallic lustre
Malleability
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v. Ductility
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vi. Tensile strength

vii. Elasticity
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Bond Characteristics
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Bond Length
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When atoms come closer to each other, attraction takes place between them and ,therefore, the
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potential energy of the system keeps on decreasing till at a particular distance, the potential energy
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is minimum.

If the atoms are further brought closer ,the repulsion start and therefore, the potential energy of the
system begins to increase.

At equilibrium distance the atoms keep on vibrating about their mean position.

The equilibrium distance between the centres of the nuclei of the two bonded atoms is called its
Bond length

It is expressed in terms of angstrom or picometer.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

It is determined experimentally by x-ray diffraction or electron diffraction method or spectroscopic

method.

In an ionic compound ,the bond length is the sum of their ionic radii and in covalent compound, it is
the sum of their covalent radii.

For a covalent molecule AB, the bond length is given by d= ra + rb

Factors affecting Bond length

1) Size of the atoms

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The bond length increases with increase in size of the atom.

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HI > HBr > HCl > HF

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2) Multiplicity of Bond

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The bond length decreases with the multiplicity of the bond.
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3) Type of hybridisation
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An s orbital is smaller in size, greater the s character ,shorter is the hybrid orbitals and hence shorter
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is the bond length.

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Bond enthalpy

When atoms come close together resulting in the formation of bond between them ,energy is
released.

The amount of energy required to break one mole of bonds of a particular type so as to separate
them into gaseous atoms is called bond dissociation enthalpy or Bond enthalpy.

Bond enthalpy is usually expressed in KJ mol-1

Greater is the bond dissociation enthalpy ,stronger is bond.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

For diatomic molecules like H2 , Cl2, O2, N2, HCl, HBr, HI the bond enthalpies are equal to their
dissociation enthalpy and hence have fixed. In case of polyatomic molecules, since a particular type
of bond present in different molecules or even in the same molecule do not possess the same bond
enthalpy, therefore , bond enthalpy are usually the average values.

In H20 , first O-H bond enthalpy=502 Kj/mol

Second bond enthalpy= 427 KJ/mol

Average bond enthalpy = (502 + 427 ) / 2 = 464.5 KJ/mol

Factors affecting bond enthalpy

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1) Size of the atom

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Greater the size of the atom ,greater is the bond length and less is the bond dissociation enthalpy i.e.

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less is the bond strength.

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2) Multiplicity of bonds hs
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Greater is the multiplicity of the bond, greater is the bond dissociation enthalpy.
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3) Number of lone pair of electrons present

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Greater the number of lone pair of electrons present on the bonded atom ,greater is the repulsion
between the atoms and hence less is the bond dissociation enthalpy.
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4) Bond angle
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A bond is formed by the overlap of atomic orbitals. The direction of overlap gives the direction of the
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bond.
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The angle between the lines representing the direction of the bond i.e. the orbitals containing the
bonding electrons is called the bond angle.

5) Bond order

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

In lewis representation of a molecular or ion ,the number of bonds present between two atoms is
called the bond order

For odd electron molecule, as the 3 electron bond is considered as equivalent to half covalent bond,
the bond order can be fractional also.

Greater the bond order ,greater is the stability of the bond i.e. greater is the bond enthalpy.

Greater the bond order, shorter is the bond length.

Polar and Non-Polar Covalent Bond

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Non-polar covalent bonds

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If two similar atoms come close to each other and form a bond by sharing their electrons, the shared
electrons are equally attracted by the two atoms as the electronegativity of the atoms is same.

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Hence no poles are developed. This leads to the formation of completely non-polar bonds.
hs
If two hydrogen atoms form a bond, the electron pair will lie exactly in the middle between the two
at
atoms.
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The electron cloud is completely symmetrical and there is no charge separation at all.
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For Ex: Cl2 , O2 , N2 , F2

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Polar covalent bonds

When two dissimilar atoms ,having different electro negativities combined together to form a
covalent bond, the shared pair of electrons does not lie at equal distance from the nuclei of both the
bonded atom but shift towards the atom having greater electronegativity.

The more electronegative atom attracts the electrons more strongly, the distribution of electrons get
distorted i.e. the electron cloud is displaced more towards the more electronegative atom.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
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One end of the molecule, having more electronegative atom becomes slightly negatively charged
while the other end acquire slightly positive charge.

Positive and negative poles are developed and this type of bond is called polar covalent bond.

For Ex: HCl molecule

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Chlorine is more electronegative than hydrogen. So the force of attraction, on the shared pair
hs
,exerted by chlorine is more than that by the hydrogen. Chlorine becomes slightly negatively charged
and hydrogen become slightly positively charged.
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In symmetrical molecules like CO2 , CCl4 , although there are a number of polar bonds present, yet a
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molecule on the whole or non-polar. This is because the polar bonds cancel the effect of each other.
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Partial ionic character of covalent bonds

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

If two atoms linked together have different electro negativities ,the bond formed is polar.

The bond is said to possess partial ionic character.

The extent of partial ionic character is determined by the difference in electronegativity of the
combining atoms. More is the difference in electronegativity, greater will be the ionic character.

1) If electronegativity difference between two atoms is 1.9, the bond is said to have 50% ionic
character and 50% covalent character.

2)If the electronegativity difference between the two atoms is more than 1.9 ,the partial ionic
character of the bond is more than 50% and the bond is taken as ionic.

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3) If the electronegativity difference between two atoms is less than 1.9 ,the bond is predominantly

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covalent.

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Dipole Moments

a
hs
In a polar molecule, there are two poles present in the molecule. Hence, the molecule is said to
possess an electric dipole. Since the molecule as a whole is electrically neutral ,the negative charges
at
is always equal in magnitude to the positive charge.
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The product of magnitude of negative or positive charge(q) and the distance between the centres of
ita

the positive and negative charges is called dipole moment.

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It is usually donated by µ .
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It can be expressed as µ = q × d
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The charge q is of the order of 10-10 esu and the internuclear distance d is of the order of 10-8 cm.
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Therefore ,the dipole moment is of order 10 -18 esu cm.

In S.I. units, 1 D = 3.335 × 10 -30 Cm

Dipole moment and molecular structure

Diatomic molecules

Dipole moment is a vector quantity i.e. it has magnitude as well as direction.

As a polar diatomic molecule possesses only one polar bond, the dipole moment of that molecule is
equal to the dipole moment of the polar Bond.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

In HCl, the molecular dipole moment is equal to the dipole moment of H-Cl bond i.e 1.07 D.

Greater the electronegativity difference between the bonded atom, greater if the dipole moment.
Dipole moment of hydrogen halides are in the order :

H-F > H-Cl > H-Br > H-I

Polyatomic molecules

As a polyatomic molecule has more than one polar bond ,the dipole moment is equal to the resultant
dipole moment of all the individual bonds.

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The magnitude of resultant dipole moment not only depends upon the values of the individual dipole
moment of the bonds but also on their arrangement in space.

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Dipole moment of water is 1.84 D which is equal to the resultant dipole moment of two O-H bonds.

a la
hs
at
lp
ita

In case of ammonia ,the dipole moment of molecule i.e. 1.47 D is the resultant of the dipole moment
ig

of the individual dipole moments of N-H bonds.

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In carbon dioxide molecule, there are two polar bonds. These polar bonds possesses the same value
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of dipole moment but the overall dipole moment of molecule is found to be zero. Individual dipole
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moment in this molecule are of equal magnitude but their directions are opposite to each and hence
cancel out.
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In symmetrical molecules like Boron trifluoride ( BF3) Methane ( CH4) and carbon tetrachloride
(CCl4), the molecular dipole moment is found to be zero. Individual dipole moments cancel out on
account of the symmetry of the molecule. In BF3 ,the resultant of two bond moments being equal
and opposite to that of the third cancel out.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

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a la
hs
at
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CHCl3 is also tetrahedral but has a dipole moment of 1.04.

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Dipole moment of NH3 and NF3

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Both NH3 and NF3 molecules have pyramidal shape with one lone pair of electrons on N atom. As
fluorine is highly electronegative, it appears that N-F bond should be more polar and the net dipole
moment of NF3 should be much greater than that of NH3.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

The dipole formed between the lone pair and nitrogen atom has to be taken into consideration
which is in the direction of the lone pair.

F is more electronegative than nitrogen ,therefore direction of bond is from nitrogen to fluorine
whereas nitrogen is more electronegative than hydrogen, the direction of bond is from hydrogen to
nitrogen.

Resultant moment of N-H bond adds up to the bone moment of the lone pair, that of 3 N-F bonds
partly cancel the resultant of the lone pair. Hence the net dipole moment of NF 3 is less than that of
NH3.

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Application of dipole moment

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1) In determining the polarity of bonds :

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Greater is the magnitude of dipole moment, higher will be the polarity of the bond.This is applicable

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to molecules containing only one polar bond.In case of non-polar molecules like H2 , O2, N2 etc.

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the dipole moment is found to be zero .This is because there is no charge separation in these
molecules. hs
at
2) In determining the symmetry of the molecules
lp

If any molecule possesses two or more polar bonds ,it will not be symmetrical if it possesses some
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molecular dipole moment.

ig

Water µ = 1.84 D
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H2S µ = 0.95 D
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NH3 µ = 1.47 D
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(w

If a molecule contains a number of similar atoms linked to the central atom and the overall dipole
moment of the molecule is found to be zero ,this will imply that the molecule is symmetrical.

For Ex: BF3 , CH4 , CCl4

3) To distinguish between cis and trans isomers

Cis isomer usually has higher dipole moment than trans isomer.

4) To distinguish between Ortho, meta and para isomers

The dipole moment of para isomer is zero and that of ortho is greater than that of meta.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

Fajan’s Rules

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When a cation approaches an anion, the electron cloud of the anion is attracted towards a cation

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and hence gets distorted. The effect is called polarisation of the anion.

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The power of cation to polarise anion is called its polarising power and tendency of the anion to get
polarised is called polarisability. The greater is the polarisation produced, more is the neutralisation

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of the charges and hence the ionic character decreases or the covalent character increases.

a
hs
The polarising power of the cation and the polarisability of the anion and hence the formation of
covalent bond depends on:
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1) Small size of the cation
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Smaller the cation, greater is its polarising power.

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2) Large size of the anion

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larger the anion, greater is its polarisability. Covalent character of lithium halides is in the order:
w

LiI > LiBr > LiCl > LiF

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3) Large charge on the cation or anion

Larger the charge on the cation, greater is its polarising power. Hence covalent character increases .

The covalent character of the chlorides is in the order:

NaCl < MgCl2 < AlCl3

Greater the charge on the anion, more easily it gets polarised .

4) Electronic configuration of the cations

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

If two cations have the same size and charge, then the one with 18 electrons in the outermost shell
has greater polarising power than the other with 8 electrons in the outermost shell.

Characteristics of covalent compounds

1) Physical States: The covalent compounds exist in all the three states i.e. solid ,liquid and gases.

2) Crystal structure :The crystal structure of covalent compounds differ from that of ionic
compounds. They usually consists of molecules rather than ions.

3) Melting and boiling point: Covalent compounds have low melting and boiling point because the
molecules in covalent compounds are held together less rigidly.

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4) Solubility: They are generally soluble in organic solvents but insoluble in water and other polar

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solvents.

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5) Electrical conductivity :Since there are no free ions in covalent compounds to conduct electricity,

a
they are bad conductors of electricity.
hs
6) Non-ionic reactions :These compounds are molecular in nature and not ionic, their reactions are
at
molecular and proceed at a much slower rate than those of ionic compounds.
lp

7) Directional characteristics and isomerism: As the atoms in covalent compounds are held together
ita

by the shared electrons ,it is rigid and directional. Hence, atoms in a molecule can take up different
directional arrangement and thus show structural and stereoisomerism.
ig

Shapes Of Molecules
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w

Shape of beryllium fluoride( BeF2) molecule

w

Atomic number of Be = 4
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Electronic configuration in ground state is 1s2 2s2

Electronic configuration in excited state is 1s2 2s1 2px1

one 2s orbital and one 2p orbital undergo sp hybridisation to form two half filled sp hybrid orbitals
which are oriented at an angle of 180°.

They overlap with the half filled orbitals of the two fluorine atoms to give a linear shape.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

Shape of Boron trifluoride (BF3) molecule

Atomic number of Boron=5

Electronic configuration in ground state 1s2 2s2 2px 1

)
m
Electronic configuration in excited state = 1s2 2s1 2px1

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One 2s and two 2p orbitals undergo sp2 hybridisation to form 3 half filled hybrid orbitals which are

la
planar and oriented at an angle of 120° to each other. These overlap with half filled orbitals of 3
fluorine atoms to form BF3 which has triangular planar shapes.

a
hs
at
lp
ita
ig
.d
w
w
(w

Shape of Methane ( CH4 )molecule

Atomic number of carbon = 6

Electronic configuration in the ground state is 1s2 2s2 2px 1 2py1

Electronic configuration in the excited state is 1s2 2s1 2px1 2py1 2pz1

One 2s and three 2p orbitals undergo sp3 hybridisation to form four sp3 hybrid orbitals which are
arranged tetrahedrally at an angle of 109°28´to each other.

(25)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

The 4 sp3 hybrid orbitals overlap with the half filled 1s orbital of 4 hydrogen atoms ,forming CH4.

)
m
.co
la
Shape of Ethane molecule(C2H6)

a
hs
In the formation of ethane molecule, each carbon atom undergoes sp3 hybridisation ,thus forming
at
four sp3 hybrid orbitals directed towards the corners of a tetrahedron and inclined to each other at
an angle of 109°28.
lp
ita

One sp3 hybrid orbital of the first carbon atom undergoes overlapping with one sp3 hybrid orbitals of
second carbon atom along the internuclear axis ,thus forming a sigma bond between them.
ig

The remaining 3 sp3 hybrid orbitals of each carbon atom undergo overlapping with the half filled 1s
.d

orbital of hydrogen atom, each along internuclear axis and hence forming sigma bond.
w
w
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(26)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

)
m
.co
a la
Shape of ethylene molecule (C2H4) hs
at
The electronic configuration of carbon atom in the excited state is 1s2 2s1 2px1 2py1 2pz1
lp

Each carbon atom undergoes sp2 hybridisation, thus leaving one 2pz orbital is the unhybridized state.
ita

The 3 sp2 hybrid orbitals of each carbon atom are planar and are inclined to each other at an angle of
120°.
ig
.d

One sp2 hybrid orbital of the the first carbon atom overlaps with one sp2 hybrid orbital of the second
w

carbon atom along the internuclear axis thereby forming one sigma bond between them.
w

The other two sp2 hybrid orbitals of each carbon atom overlap with the half filled 1s orbital of
(w

hydrogen atom along their respective internuclear axis forming sigma bond.

The unhybridized 2pz orbital of the first carbon atom undergoes sideways overlapping with the
unhybridized 2pz orbitals of the second carbon atom, thereby forming a π bond between the two
carbon atoms. The two carbon atoms are linked to each other by 1 sigma bond and 1 π bond and
each carbon atom is further linked to two hydrogen atoms by sigma bond. The molecule is planar.

(27)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

)
m
.co
a la
Shape of acetylene molecule
hs
at
In the formation of acetylene molecule, each carbon atom undergoes sp hybridization leaving two 2p
lp

orbitals in the original unhybridised state. The two sp hybrid orbitals of each carbon atom are linear
ita

i.e. they are 180° degree apart.

ig

One sp hybrid of the first carbon atom overlaps with one sp hybrid orbital of the second carbon atom
along the internuclear axis thus forming sigma bond between them. The second sp hybrid orbital of
.d

each carbon atom overlaps with half filled 1s orbital of hydrogen atom again along the internuclear
w

axis and thus forming Sigma bonds.

w

The unhybridised 2py orbital of the first carbon atom undergoes sideways overlapping with the 2py
(w

orbital of the second carbon atom, thereby forming a π bond between the two carbon atoms.

All the carbon and hydrogen atoms are linear and there is electron cloud above and below, in the
front and at the back of the C-C axis.

(28)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

)
Summary

m
.co
1. Chemical Bond: The force of attraction which holds various chemical entities in different
species.

la
2. Electrovalent Bond : The attractive force between the oppositely charged ions which comes

a
into existence by the transference of electrons.
hs
3. Electrovalency: The number of electrons which an atom loses or gains while forming ionic
at
or electrovalent bond.
lp

4. Covalent Bond: The bond comes into existence by the mutual sharing of electrons by the
ita

atoms participating in bonding.

5. Valence Bond Approach of Covalent Bond: The bond is formed by the overlapping of
ig

halffilled atomic orbitals having electrons with opposite spins.

.d

6. Covalency: The number of half-filled atomic orbitals which an atom provides for
w

participation in overlapping at the time of bonding.

w

7. Dative Bond or Co-ordinate Bond: The bond is formed by sharing of electrons in which the
(w

shared pair of electrons is contributed by one of the atom called donor while the other
atom is called acceptor.
8. Hybridisation: The process of mixing or merging of orbitals (of slightly different energies) of
an atom to form another set of orbitals with equivalent shape and energy.
9. Geometry of the Molecule: The definite relative arrangement of the bonded atoms in a
molecule.
10. Regular and Irregular Geometry: The molecule is said to possess regular geometry if the
repulsive interactions among the electron pair around the central atom are of equal
magnitude. If the repulsive interactions among the electron pairs are unequal, the
geometry is referred to as irregular.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

11. Electronegativity: The power of an atom to attract bonding pair of electrons towards itself.
12. Dipole Moment (μ): A vector quantity defined by the product of charge developed on any
of the atom and distance between the atoms; creating a dipole.
13. Polar and Non-Polar Molecules: The molecules with dipole moment (μ) > 0 are called polar
molecules while those with μ = 0 are non-polar molecules.
14. Dipole-Dipole Interactions: The attractive interactions among the opposite ends of polar
molecules in liquid and solid state.
15. Hydrogen Bond: The electrostatic force of attraction between covalently bonded H-atom of
one molecule and the electronegative atom (F or N or O) of the other molecule.

)
m
16. Resonance: When a molecule is represented by more than one electronic arrangement
none of which is able to explain the observed characteristics of the molecule, then the

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actual structure is intermediate of various electronic arrangements and is known as
resonance hybrid. The various electronic arrangements are called resonating structures or

la
canonical structure.

a
hs
17. Molecular Orbital Theory (MOT): According to this theory, in molecules the electrons are
present in new orbitals called molecular orbitals. Molecular orbitals are not associated with
at
a particular atom but belong to nuclei of all the atoms constituting the molecule.
lp

18. LCAO Method: This is an approximate method, according to which the molecular orbitals
are obtained by linear combination of atomic orbitals.
ita
ig
.d
w
w
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(30)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

)
m
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a la
hs
at
lp
ita
ig
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w
w
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(31)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

Important Questions
Multiple Choice questions-
Question 1. Based on VSEPR theory, the number of 90° F-Br-F angles in BrF5 is
(a) 0
(b) 2
(c) 4
(d) 8
Question 2. The hybrid state of Sulphur in SO2 molecule is:

)
m
(a) sp²

.co
(b) sp³
(c) sp

la
(d) sp³d

a
hs
Question 3. In allene (C3H4), the type(s) of hybridization of the carbon atoms is (are)
(a) sp and sp³
at
(b) sp and sp²
lp

(c) Only sp²

ita

(d) sp² and sp³

ig

Question 4. The state of hybridization of the central atom and the number of lone pairs over
the central atom in POCl3 are
.d

(a) sp, 0
w

(b) sp², 0
w

(c) sp³, 0
(w

(d) dsp², 1
Question 5. The charge/size ratio of a cation determines its polarizing power. Which one of
the following sequences represents the increasing order of the polarizing order of the
polarizing power of the cationic species, K+, Ca2+, Mg2+, Be2+?
(a) Ca2+ < Mg2+ < Be+ < K+
(b) Mg2+ < Be2+ < K+ < Ca2+
(c) Be2+ < K+ < Ca2+ < Mg2+
(d) K+ < Ca2+ < Mg2+ < Be2+
Question 6. Which one of the following does not have sp² hybridized carbon?

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

(a) Acetone
(b) Acetic acid
(c) Acetonitrile
(d) Acetamide
Question 7. Which one of the following is paramagnetic?
(a) NO+
(b) CO
(c) O2–

)
(d) CN

m
Question 8. Which of the following structures will have a bond angle of 120° around the

.co
central atom?
(a) Linear

a la
(b) Tetrahedral
(c) Triangular
hs
at
(d) Square planar
lp

Question 9. An atom of an element A has three electrons in its outermost orbit and that of B
has six electrons in its outermost orbit. The formula of the compound between these two will
ita

be
(a) A3 B6
ig

(b) A2 B3
.d

(c) A3 B2
w

(d) A2 B
w

Question 10. In which of the following, the angle around the central atom is largest?
(w

(a) CS2
(b) SF4
(c) SO2
(d) BBR3
Question 11. Based on lattice enthalpy and other considerations which one the following alkali
metals chlorides is expected to have the higher melting point?
(a) RbCl
(b) KCl

(33)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

(c) NaCl
(d) LiCl
Question 12. In which of the following substances, the intermolecular forces are hydrogen
bonds?
(a) Hydrogen Chloride
(b) Hydrogen Sulphide
(c) Dry Ice
(d) Ice

)
Question 13. Which one of the following pairs of species have the same bond order?

m
(a) CN− and NO+

.co
(b) CN− and CN+
(c) O2− and CN−

la
(d) NO+ and CN+

a
hs
Question 14. Dipole-induced dipole interactions are present in which of the following pairs?
at
(a) H2O and alcohol
lp

(b) Cl2 and CCl4

(c) HCl and He atoms
ita

(d) SiF4 and He atoms

ig

Question 15. In allene (C3H4), the type(s) of hybridisation of the carbon atoms is (are)
.d

(a) Sp and sp³

w

(b) Sp and sp²

w

(c) Only sp²

(w

(d) sp² and sp³

Very Short:
1. What change in energy takes place when a molecule is formed from its atoms?
2. Arrange the following in order of increasing bond strengths.
3. Name the shapes of the following molecules: CH4, C2H2, CO2.
4. Arrange the following in order of increasing strengths of hydrogen bonding O, F, S, Cl, N
5. Identify the compound/compounds in the following in which S does not obey the Octet
rule: SO2, SF2, SF4, SF6.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

6. Name one compound each involving sp3, sp2, sp hybridization.

7. s-s, s-p, p-p form a bond, and only p-p form π bond.

Short Questions:
1. Which out of CH3F and CH3Cl has a higher dipole moment and why?
2. Define the term chemical bond. What are its different types?
3. Why covalent bonds are called directional bonds whereas ionic bonds are called non-
directional?
4. AlF3 is a high melting solid whereas SiF4 is a gas. Explain why?

)
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5. Using the VSEPR theory identifies the type of hybridization and draw the structure of

.co
OF2 What are oxidation states of O and F?
6. Account for the following: The experimentally determined N-F bond length in NF3 is

la
greater than the sum of the single covalent radii of N and F.

a
Long Questions: hs
at
1. State with reasons, which is more polar CO2 or N2O?
2. Out of peroxide ion (O2) and superoxide ion (O2) which has larger bond length and why?
lp

3. Explain the formation of the following molecules according to the orbital concept, F2, HF,
ita

O2, H2O, N2, NH3 molecules.

ig

4. What is a hydrogen bond, what are its causes, and give the conditions for hydrogen
bonding? What is the strength of hydrogen bonding? Describe the two types of hydrogen
.d

bonding.
w

Assertion Reason Questions:

w
(w

1. In the following questions, a statement of Assertion (A) followed by a statement of

Reason (R) is given. Choose the correct option out of the choices given below each
question.

Assertion (A) : Sodium chloride formed by the action of chlorine gas on

sodium metal is a stable compound.
Reason (R) : This is because sodium and chloride ions acquire octet in
sodium chloride formation.
(i) A and R both are correct, and R is the correct explanation of A.
(ii) A and R both are correct, but R is not the correct explanation of A.

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

(iii) A is true but R is false.

(iv) A and R both are false.

2. In the following questions, a statement of Assertion (A) followed by a statement of

Reason (R) is given. Choose the correct option out of the choices given below each
question.
Assertion (A) : Though the central atom of both NH3 and H2O molecules are
sp3 hybridised, yet H–N–H bond angle is greater than that of
H–O–H.

)
Reason (R) : This is because nitrogen atom has one lone pair and oxygen

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atom has two lone pairs.

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(i) A and R both are correct, and R is the correct explanation of A.
(ii) A and R both are correct, but R is not the correct explanation of A.

a la
(iii) A is true but R is false.
(iv) A and R both are false.
hs
at
Case Study Based Question:
lp

1. Read the passage given below and answer the following questions:
ita

Chemical bonding, involve interactions that account for the association of atoms into
molecules, ions, crystals, and other stable species that make up the familiar substances of
ig

the everyday world. When atoms approach one another, their nuclei and electrons interact
and tend to distribute themselves in space in such a way that the total energy is lower than
.d

it would be in any alternative arrangement. If the total energy of a group of atoms is lower
w

than the sum of the energies of the component atoms, then bond together and the energy
w

lowering is the bonding energy.

(w

The ideas that helped to establish the nature of chemical bonding came to fruition during
the early 20th century, after the electron had been discovered and quantum mechanics
had provided a language for the description of the behaviour of electrons in atoms.
However, even though chemists need quantum mechanics to attain a detailed quantitative
understanding of bond formation, much of their pragmatic understanding of bonds is
expressed in simple intuitive models. These models treat bonds as primarily of two kinds-
namely, ionic and covalent.
The type of bond that is most likely to occur between two atoms can be predicted on the
basis of the location of the elements in the periodic table, and to some extent the
properties of the substances so formed can be related to the type of bonding.
A key concept in a discussion of chemical bonding is that of the molecule. Molecules are

(36)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

the smallest unit of compounds that can exist. One feature of molecules that can be
predicted with reasonable success is their shape. Molecular shapes are of considerable
importance for understanding the reactions that compounds can undergo, and so the link
between chemical bonding and chemical reactivity is discussed briefly in this article.
(1) According to molecular orbital theory, which of the following will not be available
molecule?
(a) 𝐻𝑒22+
(b) 𝐻𝑒2+
(c) 𝐻2−

)
(d) ) 𝐻22−

m
(2) Which of the following compounds of chlorine contains both ionic as well as covalent

.co
bonds?
(a) NaCl

a la
(b) NaClO4
(c) PCl3
hs
at
(d) POCl3
(3) In 𝑃𝑂43− , the formal charge on each oxygen atom and P ꟷ O bond order respectively
lp

are:
ita

(a) - 0.75, 1.25

ig

(b) - 0.75, 1.0

.d

(c) - 0.75, 0.6

w

(d) - 3, 1.25
w

(4) On the basis of valence bond theory, the formation of H2 molecules from two H-atoms
involves.
(w

(a) The overlap of vacant is orbitals of two H-atom

(b) The lowering of potential energy of the system as the two H-atom come near to
each other
(c) The maximum energy of the system at the equilibrium internuclear distance
(d) Stabilisation of the molecule; when the nuclei are brought still closer to each other
from the equilibrium inter-nuclear distance.

2. Read the passage given below and answer the following questions:
In order to explain the shapes of molecules adequately, Sidgwick and Powell in 1940

(37)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

proposed a theory based on the repulsive interaction of the electron pairs in the valence
shell of the atoms.
Nyholm and Gillespie (1950) further developed and redefined the concept. The mai
postulates of this theory are as follows:
The number of valence shell electron pairs (bonded or non-bonded) present around the
central atom decides the shape of the molecules. The shared electron pairs are called bond
pairs and unshared or non-bonding electrons are called lone pairs. Electron pairs of valence
shell repel one another because their electron clouds are negatively charged.
These electron pairs arrange themselves in such a way so that there is minimum repulsion
and maximum distance in between them. The valence shell is considered as a sphere in

)
m
which the electron pairs are localised on the spherical surface at maximum distance from
one another.

.co
A lone pair occupies more space than a bonding pair, since it lies closer to the central
atom. This means that the repulsion between the different electron pairs follow the order:

la
Lone pair-lone pair > lone pair-bond pair > bond pair-bond pair

a
hs
at
(1) Which of the following molecule has net dipole moment zero?
lp

(a) HF
ita

(b) H2O
ig

(c) BF3
.d

(d) CHCl3
w

(2) Which one of the following species contains three bond pairs and one lone pair around
the central atom?
w

(a) H2O
(w

(b) BF3
(c) 𝑁𝐻2−
(d) PCl3
(3) Why do the deviations occur from idealised shape of H2O and NH3 molecules?
(a) Same hybridisation
(b) Different hybridisation
(c) Repulsive effect
(d) None of the above

(38)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

(4) The species, having bond angles of 120° is:

(a) PH3
(b) ClF3
(c) NCl3
(d) BCl3

Answer Key:
MCQ

)
m
1. (a) 0

.co
2. (a) Sp2

la
3. (b) Sp and sp²

a
4. (c) sp³, 0 hs
5. (d) K+ < Ca2+ < Mg2+ < Be2+
at
6. (c) Acetonitrile
lp
ita

7. (c) O2–

8. (c) Triangular
ig
.d

9. (b) A2 B3
w

10.(b) SF4
w

11.(c) NaCl
(w

12.(d) Ice

13.(d) NO+ and CN+

14.(c) HCl and He atoms

15.(b) sp and sp²

Very Short Answer:

1. There is a fall in energy.

(39)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

2. F2 < Cl2 < O2 < N2

3. CH4: Tetrahedral; C2H2: Cylindrical; CO2: linear

4. Cl < S < N < O <F.

5. SF4, SF6.

6. sp3: CH4: sp2: C2H4: sp: C2H2

7. s-s, s-p, p-p form a bond, and only p-p form π bond.

)
Short Answer:

m
.co
Ans: 1. The dipole moment of CH3Cl is greater than that of CH3F. The C-F bond length in CH3F
is smaller than the C-Cl bond length in CH3Cl. The charge separation in the C-F bond is more

la
than in the Cl-C bond- fluoride being more electronegative than chlorine. The bond length has
a greater effect than the charge separation. Hence the dipole moment of CH3C1 is greater

a
than that of CH3F. hs
at
Ans: 2. The attractive forces which hold the constituent atoms in molecules or species in
lattices etc. are called a chemical bond.
lp

They are of the following types:

ita

1. Electrovalent or ionic bond

ig

2. Covalent bond
.d

3. Coordinate or dative bond

w

4. metallic bond
5. hydrogen bond
w

6. van der Waals forces.

(w

Ans: 3. A covalent bond is formed by the overlap of half-filled atomic orbitals which have
definite directions. Hence covalent bond is directional. In ionic compounds, each ion is
surrounded by a number of oppositely charged ions and hence there is no definite direction.

Ans: 4. AlF3 is an ionic solid due to the large difference in electronegativities of Al and F
whereas SiF4 is a covalent compound and hence there are only weak van der Waal’s forces
among its molecules.

Ans: 5. The electron dot structure of OF2 is

(40)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

Thus, the central atom (O-atom) has 4 pairs of electrons (2 bond pairs and 2 lone pairs). Hence
oxygen in OF2 is sp3 hybridized and the molecule is V-shaped oxidation state of F = – 1,
oxidation state of O = + 2.

Ans: 6. This is because both N and F are small and hence have high-electron density. So they
repel the bond pairs thereby making the N-F bond length larger.

Long Answer:

)
m
Ans: 1. N2O is more polar than CO2 which is a linear molecule and thus symmetrical. Its net

.co
dipole moment is zero.

a la
hs
N2O is linear but unsymmetrical. It is a resonance hybrid of the following canonical
structures:
at
lp
ita

It has a net dipole moment of 0.116 D.

ig

Ans: 2. The bond order of O2– is 1.5 while that of O22- is 1.0.
.d

The lesser the bond order, the greater is the bond length as the bond order is inversely
w

proportional to bond length. (Hence O22- has a larger bond length than O22-.
w

Ans: 3. 1. Formation of F2 molecule. Atomic number (Z) of fluorine is 9 and its orbital
(w

electronic configuration is 1s2 2s2 2p2x, 2p2y, 2p1z. Thus, a fluorine atom has one half-filled
atomic orbital. Therefore, two atoms of fluorine combine to form the fluorine molecule as
a result of the combination for their half-filled atomic orbitals shown in Fig. The two atoms
get linked by a single covalent bond

(41)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

Formation of F2 molecule

2. Formation of HF molecule. Fluorine atom, as stated above, has one half-filled atomic
orbital. Hydrogen atom (Z = 1) has only one electron in Is orbital. Thus, the hydrogen
fluoride (HF) molecule. is formed as a result of the combination (or overlap) of the half-
filled orbitals belonging to the participating atoms.

)
m
.co
3. Formation of O2 molecules. The atomic number (Z) of oxygen is 8 and its orbital
electronic configuration is 1s2 2s2 2p2x 2p1x 2p1z. This means that an oxygen atom has

la
two half-filled orbitals with one electron each. Two such atoms will combine to form a

a
molecule of oxygen as a result of the overlap of the half-filled orbitals with opposite
spins of electrons. hs
at
lp
ita
ig
.d

Formation of O2 molecule
w

Thus, the two atoms of oxygen are bonded to each other by two covalent bonds or
w

double bonds (O = O).

(w

4. Formation of H2O molecule. In the formation of the H2O molecule, the two half-filled
orbitals of the oxygen atom combine with the half-filled orbitals (1s) of the hydrogen
atoms. Thus, the oxygen atom gets linked to the two hydrogen atoms by single covalent
bonds as shown in

(42)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

Formation of H2O molecule

)
5. Formation of N2 molecule. The atomic number of nitrogen is 7 and its orbital electronic

m
configuration is 1s2 2s2 2p1x 2p1y 2p1 z. This shows that the nitrogen atom has three

.co
half-filled atomic orbitals. Two such atoms combine as a result of the overlap of the
three half-filled orbitals and a triple bond gets formed (N = N)

a la
hs
at
lp
ita

Formation of N2 molecule
ig

6. Formation of NH3 molecule. In the formation of ammonia (NH3) molecule, three half-
.d

filled orbitals present in the valence shell of nitrogen atom combine with 1s orbital of
w

three hydrogen atoms with one electron each. As a result, the nitrogen atom completes
its octet and a molecule of NH3 is formed in which the nitrogen atom is linked to three
w

hydrogen atoms by covalent bonds.

(w

Formation of NH3 molecule

Ans: 4. When hydrogen is connected to small highly electronegative atoms such as F, O, and N
in such cases hydrogen forms an electrostatic weak bond with an electronegative atom of

(43)
 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

the second molecule, this type of bond binds the hydrogen atom of one molecule and the
electronegative atom of the 2nd molecule is called as hydrogen bond. It is a weak bond
and it is denoted by dotted lines e.g., in HF, hydrogen forms a weak bond with the
electronegative F atom of the 2nd molecule neighboring HF.

So it means hydrogen is acting as a bridge between two molecules by one covalent bond
and the other by a hydrogen bond. Due to this hydrogen bonding, HF will not exist as a
single molecule but it will exist as an associated molecule (HF)n. So hydrogen bond may

)
be defined as a weak electrostatic bond that binds the hydrogen atom of one molecule

m
and electronegative bond atoms (F, O, N) of the second neighboring molecule.

.co
Cause of hydrogen bonding: When a hydrogen atom is bonded to an electronegative atom
(say F, O, N) through a covalent bond, due to electronegativity difference, the

la
electronegative atom attracts the shared pair of electrons towards its side with a great

a
force as a result of which the shared pair of electrons will be displaced toward
hs
electronegative atom and away from a hydrogen atom.
at
Due to which hydrogen atom will acquire a slightly negative charge and if another molecule
lp

is brought nearer to it in such a way that electronegative atom of the second molecule
faces hydrogen atom of the 1st molecule, due to opposite charges present on the
ita

atoms, an electrostatic bond will be formed between the hydrogen atom of one
molecule and electronegative atom of 2nd molecule and this is called as hydrogen
ig

bond.
.d
w
w

Conditions for hydrogen bonding. The following two necessary conditions for hydrogen
(w

bonding are:

1. Hydrogen atom should be connected to highly electronegative atom say F, O, or N.

2. The electronegative atom of which the hydrogen atom is connected should be the
same in size.

The smaller The size of the electronegative atom greater will be the attraction of that atom
for shared pair of electrons and hence that pair will be displaced more nearer to that
atom and hence that atom will develop greater negative charge and the hydrogen atom
will develop a greater positive charge and hence hydrogen atom of this molecule will
easily attract negative atom of the Ian molecule and hence a hydrogen bond will be

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

easily formed.

As both these conditions are satisfied only by F, O, N atoms so only three atoms show
hydrogen bond.

Strength of Hydrogen Bond: A hydrogen bond is a very weak bond. It is weaker than an
ionic or a covalent bond. Its strength ranges from 13 kJ mol-1 to 42 kJ mol-1. The
strength of the hydrogen bond for some of the molecules is the order H-F H (40 kJ mol-
1) > O-H…… O (28 kJ mol-1) > H-N…… H (13 kJ mol-1) whereas the strength of a covalent
bond is quite high. For example, the bond strength of the H-H bond in H2 is 433 kJ mol-1

)
Types of H-bonding

m
There are two types of hydrogen-bonds

.co
1. Intermolecular hydrogen bond. It is formed between two different molecules of the

la
same or different compounds. For example H-bond in case of HF, alcohol, or water.

a
hs
2. Intramolecular Hydrogen bond. It is formed when a hydrogen atom is in between the
two highly electronegative (F, O, N) atoms present within the same molecule. For
at
example, in o-nitrophenol, hydrogen is in between the two oxygen atoms.
lp
ita
ig
.d

Assertion Reason Answer:

w
w

1. (i) A and R both are correct, and R is the correct explanation of A.

(w

2. (i) A and R both are correct, and R is the correct explanation of A.

Case Study Answer:

1. Answer:

(1) (d) ) 𝐻22−

(2) (b)NaClO4
(3) (a) - 0.75, 1.25
(4) (b) The lowering of potential energy of the system as the two H-atom come near to

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 CHEMICAL BONDING AND MOLECULAR STRUCTURE
04

each other

2. Answer:

(1) (c) BF3

(2) (d) PCl3
(3) (c) Repulsive effect
(4) (d) BCl3

)
m
.co
a la
hs
at
lp
ita
ig
.d
w
w
(w

(46)
CHEMISTRY
)
m
.co
la
CHAPTER 5: STATES OF MATTER

a
hs
at
lp
ita
ig
.d
w
w
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 STATES OF MATTER
05

STATES OF MATTER
Introduction

Gas is the state of matter in which molecules are always in random motion. Intermolecular
interactions are extremely small (almost negligible) as compared to other states like solid and
liquid. Gases are highly compressible state of matter and its state of diffusion is maximum. Gases
have their own importance in living world. Air is a gaseous mixture of oxygen, nitrogen, CO2, Ar,
etc.

)
m
Intermolecular Forces
Intermolecular forces are the forces of attraction and repulsion between interacting particles.

.co
This term does not include the electrostatic forces that exist between the two oppositely
charged ions.

a la
Van der Waal's Forces hs
at
These are the weak forces of attraction between two molecules with or without any strong
bond. These are electrostatic in nature. Types of van der Waal's forces are as follow:
lp

1. Dipole-dipole interaction: These forces exist between two molecules which are polar in
ita

nature. Opposite charges of two dipoles attract each other and produce interactions called
keesom forces. In HCl, dipole-dipole interactions exist.
ig
.d
w
w
(w

Dipole-dipole interaction energy is inversely proportional to the sixth power of the distance
between the rotating polar molecules.

(1)
 STATES OF MATTER
05

π
interaction energy ∝
r6

2. Dipole-induced dipole interaction: When a polar molecule comes closer to a non-polar

molecule it induces weak polarity (dipole) in that molecule. Now, weak interactions develop
between polar molecule and molecule in which polarity is induced. These interactions are
known as Debye interactions.

)
m
.co
a la
hs
at
3. London dispersion forces: This polar molecule produces polarity in other molecule. Weak
lp

interaction arises between instantaneous dipoles. These interactions are known as Dispersion
ita

forces or London forces.

ig
.d
w
w
(w

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 STATES OF MATTER
05

Measurable Properties of Gases

1. Temperature: Temperature is a relative measure, or indication of hotness or coldness. At
absolute zero on Kelvin scale is equivalent to –273.15°C on the Celsius scale. Both the
Celsius and the Kelvin scales have units of equal magnitude that is one degree celsius
equivalent to one kelvin.

Thus T(K) = T(°C) + 273.15

2. Pressure of a gas: According to laws of motion, pressure is defined as force applied per unit
area of surface. It is denoted by P and SI unit of it is pascal (Pa). It is a scalar quantity.

)
F

m
P=
A

.co
3. Atmospheric Pressure: The atmospheric pressure at a point is equal to the weight of a
column of air of unit cross-sectional area extending from that point to the top of the

la
atmosphere. Its value is 1.013 × 105 Pa at sea level. Atmospheric pressure is measured using

a
an instrument called barometer. hs
at
Gaseous Laws
lp

Boyle’s Law (Volume-Pressure Relation)

ita

According to this, "The volume of a given mass of gas is inversely proportional to pressure at
constant temperature." This law is given by Robert Boyle.
ig

1
.d

P ∝ … … . (at Constant T and n)

v
w

1
w

P= k
v
(w

where k is the proportionality constant.

If a fixed amount of gas at constant temperature T occupying volume V 1 at pressure P1

undergoes expansion, so that volume becomes V2 and pressure becomes P2, then according to
Boyle’s law:

P1V1 = p2V2 = constant

P1 V1
=
P2 V2

Charle’s Law (Volume-Temperature Relation)

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 STATES OF MATTER
05

According to this, "The volume of a given mass of gas is directly proportional to its absolute
temperature at constant pressure." This law is given by Jacques Charles.

V ∝ T ……. (at constant P)

V = kT

where k is the proportionality constant.

If a fixed amount of gas at constant pressure P occupying volume V1 at temperature T1

undergoes expansion, so that volume becomes V2 and temperature becomes T2, then according
to Charle’s Law:

)
m
V
= ⋯ … … . constant

.co
T
V2 T2

la
=
V1 T1

a
Gay Lussac’s Law (Pressure-Temperature Relation)hs
at
It states that at constant volume, the pressure of a fixed mass of a gas is directly proportional to
the Kelvin temperature. The law may be expressed mathematically as
lp

P ∝ T …….. (at constant V)

ita

P = kT
ig

where k is the proportionality constant.

.d
w

If a fixed amount of gas at constant volume V occupying pressure P1 at temperature T1

undergoes expansion, so that pressure becomes P2 and temperature becomes T2, then according
w

to Gay Lussac’s Law:

(w

P
= constant
T
P1 P2
=
T1 P2

Avogadro’s Law ((Volume - Amount Relationship)

According to this, “Equal volumes of all gases at same temperature and pressure contain equal
numbers of molecules”.

V∝n

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 STATES OF MATTER
05

V = kn

where k is the proportionality constant.

V1 V2
=
n1 n2

Ideal Gas Equation

On combining the Boyle’s law, Charles law and Avogadro’s law we get an equation known as
ideal gas equation which correlate P, V, T of a gas.

)
1

m
V ∝ (according to Boyle’s law at constant T)
P

.co
V ∝ T (according to Charle’s law at constant P)

la
V ∝ n (according to Avogadro’s law at constant P and T)

a
nT
V∝ hs
P

PV ∝ nT
at
lp

PV = nRT
ita

Where R is proportionality constant known as universal gas constant.

ig

Numerical value of R:
.d

➢ R = 0.0821 litre atm K–1 mol–1

w

➢ R = 0.0831 litre bar K–1 mol–1

w

➢ R = 8.314 J K–1 mol–1

(w

➢ R = 1.987 ≈ 2 cal K–1 mol–1

➢ R = 8.314 × 107 erg K–1 mol–1

If temperature, volume and pressure of a fixed amount of gas vary from T1, V1 and p1 to T2,
V2 and p2 then we can write
P1 V1 P2 V2
=
T1 T2

This equation is also known as Combined gas law.

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 STATES OF MATTER
05

Dalton’s Law of Partial Pressure

Dalton’s law of partial pressure and states that “the total pressure exerted by a mixture of non
reacting gases is equal to the sum of partial pressure of each gas present in the mixture”.

Total = p1 + p2 + p3 +......(at constant T, V)

Kinetic Theory of Gases

The postulates of kinetic theory of gases are as follows:

1. The gaseous molecules are considered to be point masses.

)
m
2. The volume of a molecule is negligible as compared to total volume of the gas.

.co
3. The molecules neither attract nor repel each other.
4. The collisions are perfectly elastic i.e. there is no loss of energy during the molecular

la
collisions.

a
5. The average kinetic energy of molecules is directly proportional to the absolute temperature
hs
of the gas.
at
6. The effect of gravity on molecular motion is negligible.
lp

The Kinetic Gas Equation

ita

where P =Pressure of the gas

ig

1
PV = mv2
.d

3
w

V = Volume of the gas

w

m = Mass of one molecule of a gas

(w

n = number of molecules of gas

u = root mean square speed of the molecule

m × n = M = molecular weight of the gas.

1
PV = Mu2
3

Graham’s Law of Diffusion

According to Graham’s Law “at constant pressure and temperature, the rate of diffusion or
effusion of a gas is inversely proportional to the square root of its vapour density or molecular

(6)
 STATES OF MATTER
05

mass”.

1
r ∝√
d

Behaviour of Real gases

Ideal gas: A gas which obeys the gas laws and the gas equation PV = nRT strictly at all
temperatures and pressures is said to be an ideal gas. But actually the concept of ideal gas is
hypothetical as there is no gas which practically is ideal. So, the non-ideal gases are the real
gases which are the actually existing gases which obey gas equation approximately only under

)
two conditions.

m
.co
(i) Low pressure.

(ii) High temperature.

a la
Causes of Deviation
hs
There are two hypothetical postulates in the kinetic theory of gases. These are as follows:
at
1. The volume of a molecule is negligible as compared to total volume of the gas. Actually, gas
lp

molecules do possess some volume which account for the deviation.

ita

2. There is no intermolecular forces of attraction between gaseous molecules.

ig

By correcting these two postulates, we get an equation which can be applied to the gases which
.d

deviate from ideal behaviour. This deviation of a gas from ideal behaviour can also be
expressed in terms of compressiblity factor (Z).
w
w

PV
Z=
RT
(w

Van der Waal’s Equation

an2
(P + V2
) (V − nb) = nRT A = πr 2

Where a and b are van der waal's constant.

Liquifaction of Gases
Gases can be liquefied by applying high pressure or by cooling.

Critical Temperature: It is the temperature above which gas cannot be liquefied, no matter how

(7)
 STATES OF MATTER
05

high be pressure.
8a
Tc =
27Rb
Critical Pressure: It is the minimum pressure that is required to liquefy a gas at critical
temperature.
a
Pc =
27b 2
Critical Volume: It is the volume occupied by gas at critical temperature and critical pressure.

)
m
Vc = 3b

.co
1. Liquid State:

It is the intermediate state between gaseous and solid states. Liquids possess fluidity like gases

la
but incompressibility like solids.

a
Properties of liquid are: hs
at
a. A liquid is made up of molecules. Only Hg(l) is in atomic state.
b. The intermolecular forces of attraction in a liquid are quite large.
lp

c. Liquids have no definite shape but have definite volume as the cohesive forces are
ita

strong.
d. Liquids diffuses slowly in comparison to gas.
ig

e. They have definite volume but irregular shapes or we can say that they can take the
.d

shape of the container.

2. Evaporation: The process of change of liquid into vapour state at any given temperature is
w

evaporation. Evaporation is accompanied by cooling as average kinetic energy of remaining

w

molecules decreases. Example: Ether evaporates faster than alcohol.

(w

3. Vapour Pressure: In a closed vessel when the rate of evaporation become equal to rate of
condensation, i.e. equilibrium is established, the pressure exerted by the vapours of liquid on
its on surface is known as vapour pressure.
4. Boiling Point: Boiling point of the liquid is the temperature at which the vapour pressure of
the liquid is equal to the atmospheric pressure. Ex- Boiling point of pure water is 100 ℃.
5. Surface tension: “It is the force acting on the surface at right angles to any line of unit
length”. The property of surface tension may also be described in terms of the tendency of a
liquid to decrease its surface area. It's SI unit is N/m.
F
Surface tension, S =
l

(8)
 STATES OF MATTER
05

)
6. Viscosity: The property of the liquids which determines their resistance to flow, is called

m
viscosity. The forces between the layers which oppose the relative motion between them are
known as the forces of viscosity. Thus viscosity may be thought of as the internal function of a

.co
fluid in motion.

la
dv
F ∝ is called velocity gradient]

a
dz

F∝A
hs
at
dv
F = nA
lp

dz
ita

η is the coefficient of viscosity. It is expressed in Nm–2s or poise

ig

1 poise = 0.1 Nm–2s

.d
w
w
(w

7. Fluidity(Φ): The reciprocal of the coefficient of viscosity is called Fluidity.

1
ᶲ=
ᶯ

1. Three different states of matter (solid, liquid and gas): Solid is that state of matter which has
a definite shape and a definite volume, liquid has a definite volume but no definite shape
whereas gas has neither definite shape nor definite volume.

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 STATES OF MATTER
05

2. Two more states of matter:

i. Plasma state which consists of a mixture of electrons and positively charged ions formed
due to super heating of gases, e.g., in sun or stars.

ii. Super cooled solid state in which atoms lose their identity to form a single super atom.

3. Triple point: It is the temperature at which all the three states of matter or phases of the
same substance exist together, e.g., ice, water and water vapour exist together at 0.01°C
(273.16 K) and 4.58 mm pressure.

4. Ideal and Real gases: A gas which obeys ideal gas equation under all conditions of

)
temperature and pressure is called an ideal gas. However, the concept of ideal gas is only

m
hypothetical. The gases obey gas laws only if pressure is low or temperature is high. Such

.co
gases are called real gases.

5. Significance of van der Waal’s constants: ‘a’ is a measure of the magnitude of attractive

la
forces whereas ‘b’ is a measure of the effective size of the gas molecules. b = 4v where v is

a
actual volume of gas molecules. ‘b’ is called excluded volume or co-volume.
hs
6. Boiling point: It is the temperature at which vapour pressure of the liquid becomes equal to
at
external pressure. When external pressure = 1 atm = 760 mm, it is called normal boiling
lp

point.
ita

7. Surface tension of liquids: It is the force acting at right angles to the surface along one
centimeter length of the surface. Its units are dynes cm–1 or Nm–1.
ig

8. Vapour pressure of a liquid: It is the pressure exerted by the vapour present in equilibrium
.d

with a liquid in a closed vessel at a particular temperature. Cooling is caused by evaporation

w

because more energetic molecules leave the liquid.

w

9. Viscosity of liquids: It is the internal resistance of a liquid to flow or it is the force of friction
(w

which one part of the liquid offers to another part of the liquid.

10. Factors affecting viscosity:

i. Nature of the liquid : Greater the inter-molecular forces, higher is the viscosity.

ii. Temperature: Viscosity of a liquid decreases with increase of temperature because

kinetic energy increases and hence inter-molecular forces of attraction decrease.

11. Boyle’s law: Temperature remaining constant, volume of a given mass of a gas is inversely
1
proportional to its pressure, i.e., V ∝ at constant T or PV = constant.
P

12. Dalton’s law of partial pressures: If two or more gases which do not react chemically with

(10)
 STATES OF MATTER
05

each other are enclosed in a vessel, then total pressure exerted by the gaseous mixture is the
sum of their partial pressure.

13. Graham’s law of diffusion/effusion: Under similar conditions of temperature and pressure,
rates of diffusion/effusion of different gases are inversely proportional to the square root of
their densities.

14. Compressibility factor (Z): The extent of deviation of a real gas from ideal behaviour is
V
expressed in terms of compressibility factor (Z) viz. Z = P RT.
n

Characteristics of Gases

)
m
Characteristics of Gases

.co
1) Gases have neither definite shape nor definite volume. They take up the shape and volume of
the container.

la
2) They have lower density than liquids and solids.

a
3) They are highly compressible
hs
at
4) Gases intermix completely in all proportion without any mechanical aid.
lp

5) They exert pressure equally in all direction.

ita

Measurement of mass
ig

The mass of a gas can be easily determined by weighing the container containing the gas, and
.d

then emptying the container by taking out the gas and weighing the empty container again. The
w

difference between the two masses gives the mass of the gas.
w
(w

1 mole = 6.022 × 1023

Measurement of volume

As a gas fills the whole of the vessel in which it is put, hence the volume of the gas is equal to the
volume of its container which in turn can be calculated from the dimensions of the container.

The S.I. unit of volume is m3.

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 STATES OF MATTER
05

1 m3 = 103 dm3 = 106 cm3

1 ml =1 cm3

1 L = 103 cm3 = 1 dm3 = 10-3 m3

Measurement of pressure

The instrument used for the measurement of atmospheric pressure is called a barometer.

)
m
.co
a la
hs
at
lp
ita
ig

It consists of inverting a tube filled with mercury in a dish of mercury. The height of the mercury
column above the level of mercury in the dish is a measure atmospheric pressure at that place.
.d
w

Mercury is used as a barometric liquid because

w

1) The height of the column in a barometer is inversely proportional to the density of the liquid.
(w

As Mercury has very high density, the height of the column setup is very convenient for study.

2) Mercury is non-volatile at room temperature. Hence, the vapour pressure due to Mercury
vapour is negligible.

The instrument used for the measurement of the pressure of a gas is called manometer. It simply
consists of a U- shaped tube containing mercury usually.

Two types of manometers are:

1)Those in which the longer limb is closed. Closed limb manometer is used only for gases at
pressure less than the atmospheric pressure.

(12)
 STATES OF MATTER
05

)
m
.co
la
2)Those in which the longer limit is open.Open limb manometer is used for all.

a
hs
at
lp
ita
ig
.d
w
w

Suppose height of the mercury column= h cm

(w

Area of cross section of the tube= A cm2

Volume of the mercury column= A × h cm3

Density of mercury at room temperature= ρ g cm-3

mass of mercury column=A × h × ρ grams

weight of mercury column= (A × h × ρ ) × g gram

Weight of mercury column is the force acting on A cm3.Hence

Pressure= h × ρ × g

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 STATES OF MATTER
05

A standard or normal atmospheric pressure is defined as the pressure exerted by a mercury

column of exactly 76 cm at 0°C. This is the pressure exerted by the atmosphere at the sea level.

1 atm= 76 cm = 760 mm = 760 torr

1 atm= 1.01325 bar

1atm= 0.987 atm

The S.I. unit of pressure is pascal(Pa)

1 Pa= 1 Nm-2 = 1kg m-1 s-2

)
m
1atm= 1.01325 × 105 Nm-2

.co
1 bar= 102 kPa

la
Measurement of temperature

a
Temperature is a measure of the extent of hotness or coldness of a body.
hs
It is based on the principle that substances expands on heating.
at
Substance used in the measurement of temperature is mercury.
lp
ita

There are three different scales on which the temperature are measured

1)Fahrenheit scale
ig
.d

2)Kelvin scale
w

3)Celsius scale
w

5 9
(w

Tk = TC + 273.15 TC = (TF − 32) TF = TC + 32

9 5
Maxwell-Boltzmann Distribution
Maxwell-Boltzmann distribution of Molecular speed

At a particular temperatures, different molecules of a gas possess different speeds. Due to

continues collision among the molecules themselves and against the walls of the container ,their
speed keep on changing.

As a result of collision, some others are speeded up, some others are slowed down and hence
the fashions of molecules possessing particular speed remain constant at constant temperature.

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 STATES OF MATTER
05

If fractions of molecules possessing particular speed are plotted against their corresponding
speeds at a particular temperature, a curve is obtained. This distribution of speed is called
maxwell-Boltzmann distribution.

)
m
.co
a la
From this curve, it may observed that,
hs
at
(1) Fraction of molecules having too low or too high-speed are very small.
lp

(2) The peak of the curve corresponds to a speed possessed by the maximum fraction or
ita

maximum number of molecules. This speed is called most probable speed and is represented by
c∗
ig
.d

Effect of nature of the gas

w

At the same temperature, lighter gas will have higher value of most probable speed i.e. move
w

faster than heavier gases.

(w

For example : Distribution curve for chlorine and nitrogen gases are:

Effect of temperature

Maxwell – Boltzmann distribution curve for a gas at three different temperatures is

(15)
 STATES OF MATTER
05

(1) The peak shift forward showing that the most probable velocity increases.

(2) The peak shift downwards showing that fraction of molecules or number of molecules

)
possessing most probable velocity decreases.

m
.co
(3) The curve is flattened in the middle showing that more molecules have speeds near to the
most probable speed.

la
(4) The fraction of molecules having higher speed increases.

a
hs
(5) The fraction of molecules having lower speed decreases.
at
Relationship between different types of speed
lp
ita
ig
.d
w
w
(w

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 STATES OF MATTER
05

Liquefaction of Gases And Critical Temperature

The liquefaction of a gas takes place when the intermolecular forces of attraction become so
high that they bind the gas molecules together to form the liquid state.

The intermolecular forces of attraction can be increased either by increasing the pressure so that
the molecules come close together or by cooling the gas so that the kinetic energy of the
molecules decreases and they become slower.

The effect of temperature on the liquefaction of gases is found to be very important as higher
the temperature of the gas ,more difficult it is to liquefy it and higher is the pressure required.

)
Gas like hydrogen ,helium, oxygen, nitrogen could not be liquefied at room temperature by

m
application of pressure alone. Each of these gases could also be liquefied provided first it is

.co
cooled down to or below a particular temperature. For each gas, there is a particular
temperature above which it cannot be liquefied, howsoever, high pressure may be applied on

la
the gas. This temperature is called critical temperature.

a
Critical temperature of a gas may be defined as that temperature above which it cannot be
hs
liquefied however high pressure may be applied on the gas.
at
The pressure required to liquefy the gas at the critical temperature is called critical pressure .
lp

The volume occupied by 1 mole of the gas at critical temperature and critical pressure is called
ita

critical volume.
ig

All the three are called critical constants of the gas and are represented by Tc, Tp, Tv.
.d

Andrews experiment on critical phenomena

w
w
(w

(17)
 STATES OF MATTER
05

)
m
.co
a la
hs
at
lp
ita
ig

Andrews in 1861 was the first to study the critical phenomena experimentally using carbon
dioxide gas.
.d
w

He studied the effect of pressure on the volume of carbon dioxide at different constant
temperature. The plots obtained are called isotherms.
w
(w

At the lowest temperature employed i.e. 13.1° C , at low pressure, carbon dioxide exist as a gas,
as shown at the point A.

As the pressure is increased, the volume of the gas decreases along the curve.

The point at which liquefaction of the gas starts, volume decreases rapidly because liquid has
much less volume than the gas.

Once the liquification is complete, the increase in pressure has very little effect upon volume
because liquids are very little compressible. Hence a steep curve is obtained.

As the temperature is increased, horizontal portion becomes smaller and smaller and at 30.98 °C
, it is reduced to a point E.

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 STATES OF MATTER
05

Above 30.98°C ,the gas cannot be liquefied at all, however high pressure may be applied. Thus
30.98°C is the critical temperature.

We get a dome shaped curve.

A point like A represent gaseous state.

A point Like D represents a liquid state.

A point within the dome shaped area represents existence of liquid and gaseous carbon dioxide
in equilibrium.

)
Importance of critical temperature

m
The critical temperature of a gas is a measure of the strength of the intermolecular forces of

.co
attraction.

la
Weaker are the intermolecular forces ,more difficult it is to liquefy that gas and hence lower

a
would be the critical temperature of that gas.
hs
Helium and hydrogen have weak intermolecular forces, thus they are difficult to liquefy and
at
hence have low critical temperature.
lp

Carbon dioxide and ammonia have strong intramolecular forces of attraction, they can be easily
liquefied and their critical temperature are high which are above room temperature.
ita

Van der waals constant a is also a measure of intermolecular forces of attraction. Hence it is
ig

found that the values of constant a increase in the same order as the critical temperature.
.d

As a gas can be liquefied below the critical temperature by applying pressure. Therefore above
w

the critical temperature ,it is a gas but below the critical temperature it is a vapour.
w

For ex: Carbon dioxide below its critical temperature is called carbon dioxide vapour.
(w

Filed Under: States of Matter, Chemistry, Class 11

Tagged With: Andrews experiment on critical phenomenon, carbon dioxide vapour, critical
constants, critical pressure, Critical temperature, critical volume, Importance of critical
temperature, isotherms, liquefaction of a gas

You are here: Home / Class 11 / Chemistry / States of Matter / Vapour Pressure

Vapour Pressure
In a liquid, the molecules are quite close together so that there are considerable forces of
attraction between them and hence they are held together in a definite volume.

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 STATES OF MATTER
05

The liquids possess fluidity like gases but incompressibility like solid.

Properties of Liquid

(1) Liquids have no definite shape: They take up the shape of the vessel in which they are put.
This is because the molecules in a liquid are in a state of constant rapid motion.

(2) Liquids have a definite volume: This is because the intermolecular forces of attraction in a
liquid are quite strong and unlike gas molecules, the liquid molecules are not completely free to
move.

(3) Liquids have much higher density than gases:This is because the molecules in a liquid are

)
quiet close together. Thus the molecules are much more closely packed than those of the gases.

m
.co
(4) Compressibility :liquids are much less compressible than gases.This is because the
intermolecular distances of separation are much smaller in liquid than that in gases.

la
(5) Diffusion: liquids diffuse like gases but the diffusion is much slower because the liquid

a
molecules are quite close, they undergo a much larger number of collisions with each other.
hs
Vapour Pressure
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Suppose some liquid is placed in an evacuated vessel connected to a manometer. According to

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 STATES OF MATTER
05

kinetic theory of liquids, the molecules of the liquid are constantly moving in different directions
with different speeds. As these molecules are moving with different speeds, they possess
different kinetic energy.

At any particular temperature ,the energy of some of the molecules may be so high that they
may overcome the forces of attraction by the neighbouring molecules and may leave the liquid
and come in the space above the liquid. This process is called evaporation

As the time passes, more and more molecules of the liquid leave the liquid and come in space
above the liquid. The molecules thus present above the liquid are called vapour. The molecules
in the vapour phase are also constantly moving and some of them strike the surface of the liquid

)
and maybe recaptured by the liquid. The process is called condensation.

m
If the liquid is added into the evacuated vessel ,then initially, as there are no molecules of

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vapour, the rate of condensation is zero.

la
If the temperature is kept constant, the evaporation continues at constant rate as shown by the
straight line plot. With the passage of time ,as a number of molecules in the vapour phase

a
hs
becomes more and more ,the rate of condensation also increases.
at
A stage is reached when rate of condensation becomes equal to rate of evaporation i.e. as many
molecules re-enter into a liquid as leave the liquid in the same time.This state is called state of
lp

equilibrium .
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The pressure exerted by the vapours at this stage is called vapour pressure or saturated vapour
pressure as the vapour phase is saturated with vapours at this stage.
ig
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Vapour pressure of a liquid at any temperature may be defined as the pressure exerted by the
vapour present above the liquid in equilibrium with the liquid at that temperature.
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Important results related with process of evaporation

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(1) Cooling caused by Evaporation

When a liquid evaporates ,the more energetic molecules leave the liquid. As a result the average
kinetic energy of the remaining liquid decreases and hence the temperature falls.

(2) Factors affecting Vapour Pressure

(i) Nature of the liquid : If the intermolecular forces of attraction in the liquid are weak ,the
molecules can easily leave the liquid and come into vapour phase and hence the vapour pressure
is higher.

For example: The vapour pressure of acetone, benzene is higher than that of water at same
temperature.

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 STATES OF MATTER
05

(ii) Effect of temperature: As the temperature of a liquid is increased, the vapour pressure of
liquid increases.

(3) Boiling point

The vapour pressure of a liquid increases as the temperature is increased. The vapour escaping
are only from the surface of the liquid. If the temperature is further increased till the vapour
pressure becomes equal to atmospheric pressure, the vapour in the form of bubbles from below
the surface start rising to the surface and escape into the air. The temperature at which this
happens is called boiling point.

Boiling

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Boiling point of a liquid is defined as the temperature at which the vapour pressure of the liquid

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becomes equals to external pressure.

When the external pressure is normal atmospheric pressure, the boiling point is called normal

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boiling point.

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hs
When the external pressure is equal to 1 bar, the boiling point is called standard boiling point of
the liquid.
at
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Standard boiling point of a liquid is slightly less than the normal boiling point because one bar is
slightly less than 1 atmosphere pressure.
ita

Application of effect of external pressure on boiling point

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(1) If the external pressure is higher, more heat will be required to make the vapour pressure
.d

equal to external pressure and hence higher will be the boiling point. That is why in hospitals ,the
w

surgical instruments are sterilised in autoclaves in which boiling point of water is raised by using
a weigh to cover the vent.
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(2) If the external pressure is decreased, the boiling point is lowered. This is the reason that a
liquid boils at a lower temperature on the top of the mountain than on the sea shore. That is
why at hills, use of pressure cooker is essential for cooking food.

(3) It is used for purifying the unstable liquids by distillation under reduced pressure.

(4) Heat of Vaporisation

When the liquid starts boiling ,if extra heat is supplied to the liquid, it is used up not in increasing
the temperature of the liquid but to overcome the intermolecular forces of attraction, existing in
the liquid and thus changing the liquid into vapour. Hence the temperature remain constant till
whole of the liquid changes into vapour.

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 STATES OF MATTER
05

The amount of heat required to change 1 mole of the liquid into its vapour at the boiling point is
called the heat of vaporisation of the liquid.

Greater the intermolecular forces of attraction present in a liquid, greater is the heat of
vaporisation and higher is the boiling point.

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a la
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 05

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STATES OF MATTER

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 STATES OF MATTER
05

Important Questions
Multiple Choice questions-
Question 1. Three containers A, B, C of equal volume contain oxygen, neon and methane
respectively at same temperature and pressure. The increasing order of their masses is
(a) A < B < C
(b) B < C < A
(c) C < A < B
(d) C < B < A

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Question 2. A gas will approach ideal behaviour at

m
(a) Low temperature, low pressure

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(b) Low temperature, high pressure

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(c) High temperature, low pressure

a
(d) High temperature, high pressure hs
Question 3. Containers A and B have same gas. Pressure, volume and temperature of A are all
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twice those of B. The ratio of number of molecules of A and B is
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(a) 1 : 2
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(b) 2 : 1
(c) 1 : 4
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(d) 4 : 1
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Question 4. According to kinetic theory of gases,in an ideal gas,between two successive

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collisions a gas molecule travels

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(a) In a circular path

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(b) In a wavy path

(c) In a straight line path
(d) With an accelerated velocity
Question 5. When did substances exist in different crystalline forms the phenomenon is called:
(a) Allotropy
(b) Polymorphism
(c) Polymerization
(d) Isomorphism
Question 6. Sl unit of pressure is :

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 STATES OF MATTER
05

(a) Pascal
(b) torr
(c) mm of Hg
(d) none of the above
Question 7. If the pressure of a gas is increased then its mean free path becomes:
(a) 0
(b) Less
(c) More

)
(d) Infinity

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Question 8. 1 atmosphere is equal to:

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(a) 1 torr

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(b) 760 cm

a
(c) 760 mm
(d) 76 torr
hs
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Question 9. Grahams law refers to :
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(a) Boiling point of water

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(b) Gaseous Diffusion

(c) Gas Compression
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(d) Volume changes of gases

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Question 10. The rise or fall of a liquid within a tube of small bore is called :
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(a) Surface Tension

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(b) Capillary Action

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(c) Viscosity
(d) Formation of Curvature
Question 11. The rates of diffusion of gases are inversely proportional to square root of their
densities . This statement refers to :
(a) Daltons Law
(b) Grahams Law
(c) Avogadros Law
(d) None of the Above
Question 12. Cooling is caused by :

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 STATES OF MATTER
05

(a) Evaporation
(b) Convection
(c) Conduction
(d) none of the above
Question 13. If helium and methane are allowed to diffuse out of the container under the
similar conditions of temperature and pressure, then the ratio of rate of diffusion of helium to
methane is:
(a) 2 : 1
(b) 1 : 2

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(c) 3 : 5

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(d) 4 : 1
Question 14. Equal masses of ethane and hydrogen are mixed in an empty container at 25°C .

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The fraction of total pressure exerted by hydrogen is

a
(a) 1 : 2 hs
(b) 1 : 1
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(c) 01 : 16
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(d) 15 : 16
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Question 15. The volume of 2.8 g of carbon monoxide at 27°C and 0.0821 atm is
(a) 30 L
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(b) 3 L
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(c) 0.3 L
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(d) 1.5 L
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Very Short:
1. What change in energy takes place when a molecule is formed from its atoms?
2. Arrange the following in order of increasing bond strengths.
3. Name the shapes of the following molecules: CH4, C2H2, CO2.
4. Arrange the following in order of increasing strengths of hydrogen bonding O, F, S, Cl, N
5. Identify the compound/compounds in the following in which S does not obey the Octet
rule: SO2, SF2, SF4, SF6.
6. Name one compound each involving sp3, sp2, sp hybridization.
7. s-s, s-p, p-p form a bond, and only p-p form π bond.

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 STATES OF MATTER
05

Short Questions:
1. Which out of CH3F and CH3Cl has a higher dipole moment and why?
2. Define the term chemical bond. What are its different types?
3. Why covalent bonds are called directional bonds whereas ionic bonds are called non-
directional?
4. AlF3 is a high melting solid whereas SiF4 is a gas. Explain why?
5. Using the VSEPR theory identifies the type of hybridization and draw the structure of
OF2 What are oxidation states of O and F?

)
6. Account for the following: The experimentally determined N-F bond length in NF3 is

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greater than the sum of the single covalent radii of N and F.

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Long Questions:

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1. State with reasons, which is more polar CO2 or N2O?

a
hs
2. Out of peroxide ion (O2) and superoxide ion (O2) which has larger bond length and why?
3. Explain the formation of the following molecules according to the orbital concept, F2, HF,
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O2, H2O, N2, NH3 molecules.
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4. What is a hydrogen bond, what are its causes, and give the conditions for hydrogen
ita

bonding? What is the strength of hydrogen bonding? Describe the two types of hydrogen
bonding.
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Assertion Reason Questions:

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1. In the following questions, a statement of Assertion (A) followed by a statement of Reason

(R) is given. Choose the correct option out of the choices given below each question.
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Assertion (A): Three states of matter are the result of balance between
intermolecular forces and thermal energy of the molecules.
Reason (R): Intermolecular forces tend to keep the molecules together but
thermal energy of molecules tends to keep them apart.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A is false but R is true.
2. In the following questions, a statement of Assertion (A) followed by a statement of Reason

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 STATES OF MATTER
05

(R) is given. Choose the correct option out of the choices given below each question.

Assertion (A): At constant temperature, pV vs V plot for real gases is not a straight line.
Reason (R) : At high pressure all gases have Z > 1 but at intermediate pressure most gases
have Z < 1.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A is false but R is true.

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Case Study Based Question:

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1. Intermolecular forces are the forces of attraction and repulsion that exist between
molecules of a compound. These cause the compound to exist in a certain state of matter
– solid, liquid or gas and affect the melting and boiling points of compounds as well as the

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solubilities of one substance in another. Attractive intermolecular forces are also called

a
van der Waals’ forces. These are weak forces.
hs
(1) Dipole-dipole forces act between the molecules possessing permanent dipole. Ends of
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dipoles possess ‘partial charges’. The partial charge is:
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(a) More than unit electronic charge

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(b) Equal to unit electronic charge

(c) Less than unit electronic charge
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(d) Double the unit electronic charge

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(2) The nature of inter-particle forces in benzene is:

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(a) Dipole-dipole interaction

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(b) Dispersion force

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(c) Ion-dipole interaction

(d) H-bonding.
(3) The interaction energy between two temporary dipoles is proportional to (where r is
the distance between the two particles)
(a) 1/r4
(b) 1/r2
(c) 1/r5
(d) 1/r6
(4) Attractive intermolecular forces known as van der Waals forces do not include which of

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 STATES OF MATTER
05

the following types of interactions?

(a) London forces
(b) Dipole-dipole forces
(c) Ion-dipole forces
(d) Dipole-induced dipole forces
(5) In which of the following molecules, the van der Waals forces are likely to be the most
important in determining the m.pt. and b.pt?
(a) CO

)
(b) H2S

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(c) Br2

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(d) HCl
2. If a hydrogen atom is bonded to a highly electronegative element such as fluorine, oxygen,

la
nitrogen, then the shared pair of electrons lies more towards the electronegative element.

a
This leads to a polarity in the bond in such a way that a slight positive charge gets
hs
developed on H-atom, viz
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lp
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Such a bond between the hydrogen atom of one molecule and the more electronegative
atom of the same or another molecule is called a hydrogen bond.
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(1) Which of the following compounds can form hydrogen bond?

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(a) CH4
w

(b) H2O
w

(c) NaCl
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(d) CHCl3
(2) The boiling point is not affected due to hydrogen bonding in:
(a) Water
(b) Ammonia
(c) Methyl alcohol
(d) Hydrogen chloride
(3) Unusual high b.p. of water is result of:
(a) Intermolecular hydrogen bonding
(b) Intramolecular hydrogen bonding

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 STATES OF MATTER
05

(c) Both intra and intermolecular hydrogen bonding

(d) High specific heat
(4) Which of the following statements is not true?
(a) Intermolecular hydrogen bonds are formed between two different molecules of
compounds.
(b) Intramolecular hydrogen bonds are formed between two different molecules of the
same compound.
(c) Intramolecular hydrogen bonds are formed within the same molecule.
(d) Hydrogen bonds have a strong influence on the physical properties of a compound.

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Answer Key:

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MCQ

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1. (a) 0

2. (a) Sp2
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3. (b) Sp and sp²
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4. (c) sp³, 0
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5. (d) K+ < Ca2+ < Mg2+ < Be2+

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6. (c) Acetonitrile
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7. (c) O2–
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8. (c) Triangular
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9. (b) A2 B3

10.(b) SF4

11.(c) NaCl

12.(d) Ice

13.(d) NO+ and CN+

14.(c) HCl and He atoms

15.(b) sp and sp²

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 STATES OF MATTER
05

Very Short Answer:

1. There is a fall in energy.

2. F2 < Cl2 < O2 < N2

3. CH4: Tetrahedral; C2H2: Cylindrical; CO2: linear

4. Cl < S < N < O <F.

5. SF4, SF6.

)
6. sp3: CH4: sp2: C2H4: sp: C2H2

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7. s-s, s-p, p-p form a bond, and only p-p form π bond.

la
Short Answer:

a
Ans: 1. The dipole moment of CH3Cl is greater than that of CH3F. The C-F bond length in CH3F is
hs
smaller than the C-Cl bond length in CH3Cl. The charge separation in the C-F bond is more than in the
at
Cl-C bond- fluoride being more electronegative than chlorine. The bond length has a greater effect
than the charge separation. Hence the dipole moment of CH3C1 is greater than that of CH3F.
lp
ita

Ans: 2. The attractive forces which hold the constituent atoms in molecules or species in lattices etc.
are called a chemical bond.
ig

They are of the following types:

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1. Electrovalent or ionic bond

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2. Covalent bond
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3. Coordinate or dative bond

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4. metallic bond
5. hydrogen bond
6. van der Waals forces.

Ans: 3. A covalent bond is formed by the overlap of half-filled atomic orbitals which have definite
directions. Hence covalent bond is directional. In ionic compounds, each ion is surrounded by a
number of oppositely charged ions and hence there is no definite direction.

Ans: 4. AlF3 is an ionic solid due to the large difference in electronegativities of Al and F
whereas SiF4 is a covalent compound and hence there are only weak van der Waal’s forces
among its molecules.

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 STATES OF MATTER
05

Ans: 5. The electron dot structure of OF2 is

Thus, the central atom (O-atom) has 4 pairs of electrons (2 bond pairs and 2 lone pairs). Hence
oxygen in OF2 is sp3 hybridized and the molecule is V-shaped oxidation state of F = – 1,
oxidation state of O = + 2.

Ans: 6. This is because both N and F are small and hence have high-electron density. So they
repel the bond pairs thereby making the N-F bond length larger.

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Long Answer:

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Ans: 1. N2O is more polar than CO2 which is a linear molecule and thus symmetrical. Its net

la
dipole moment is zero.

a
hs
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N2O is linear but unsymmetrical. It is a resonance hybrid of the following canonical
lp

structures:
ita
ig

It has a net dipole moment of 0.116 D.

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Ans: 2. The bond order of O2– is 1.5 while that of O22- is 1.0.
w
w

The lesser the bond order, the greater is the bond length as the bond order is inversely
proportional to bond length. (Hence O22- has a larger bond length than O22-.
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Ans: 3. 1. Formation of F2 molecule. Atomic number (Z) of fluorine is 9 and its orbital
electronic configuration is 1s2 2s2 2p2x, 2p2y, 2p1z. Thus, a fluorine atom has one half-filled
atomic orbital. Therefore, two atoms of fluorine combine to form the fluorine molecule as
a result of the combination for their half-filled atomic orbitals shown in Fig. The two atoms
get linked by a single covalent bond

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 STATES OF MATTER
05

Formation of F2 molecule

2. Formation of HF molecule. Fluorine atom, as stated above, has one half-filled atomic
orbital. Hydrogen atom (Z = 1) has only one electron in Is orbital. Thus, the hydrogen
fluoride (HF) molecule. is formed as a result of the combination (or overlap) of the half-

)
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filled orbitals belonging to the participating atoms.

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a la
hs
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3. Formation of O2 molecules. The atomic number (Z) of oxygen is 8 and its orbital
lp

electronic configuration is 1s2 2s2 2p2x 2p1x 2p1z. This means that an oxygen atom has
two half-filled orbitals with one electron each. Two such atoms will combine to form a
ita

molecule of oxygen as a result of the overlap of the half-filled orbitals with opposite
spins of electrons.
ig
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Formation of O2 molecule

Thus, the two atoms of oxygen are bonded to each other by two covalent bonds or
double bonds (O = O).

4. Formation of H2O molecule. In the formation of the H2O molecule, the two half-filled
orbitals of the oxygen atom combine with the half-filled orbitals (1s) of the hydrogen
atoms. Thus, the oxygen atom gets linked to the two hydrogen atoms by single covalent
bonds as shown in

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 STATES OF MATTER
05

Formation of H2O molecule

)
5. Formation of N2 molecule. The atomic number of nitrogen is 7 and its orbital electronic

m
configuration is 1s2 2s2 2p1x 2p1y 2p1 z. This shows that the nitrogen atom has three

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half-filled atomic orbitals. Two such atoms combine as a result of the overlap of the
three half-filled orbitals and a triple bond gets formed (N = N)

a la
hs
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lp
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Formation of N2 molecule
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6. Formation of NH3 molecule. In the formation of ammonia (NH3) molecule, three half-
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filled orbitals present in the valence shell of nitrogen atom combine with 1s orbital of
w

three hydrogen atoms with one electron each. As a result, the nitrogen atom completes
its octet and a molecule of NH3 is formed in which the nitrogen atom is linked to three
w

hydrogen atoms by covalent bonds.

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Formation of NH3 molecule

Ans: 4. When hydrogen is connected to small highly electronegative atoms such as F, O, and N
in such cases hydrogen forms an electrostatic weak bond with an electronegative atom of

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 STATES OF MATTER
05

the second molecule, this type of bond binds the hydrogen atom of one molecule and the
electronegative atom of the 2nd molecule is called as hydrogen bond. It is a weak bond
and it is denoted by dotted lines e.g., in HF, hydrogen forms a weak bond with the
electronegative F atom of the 2nd molecule neighboring HF.

So it means hydrogen is acting as a bridge between two molecules by one covalent bond
and the other by a hydrogen bond. Due to this hydrogen bonding, HF will not exist as a
single molecule but it will exist as an associated molecule (HF)n. So hydrogen bond may

)
be defined as a weak electrostatic bond that binds the hydrogen atom of one molecule

m
and electronegative bond atoms (F, O, N) of the second neighboring molecule.

.co
Cause of hydrogen bonding: When a hydrogen atom is bonded to an electronegative atom
(say F, O, N) through a covalent bond, due to electronegativity difference, the

la
electronegative atom attracts the shared pair of electrons towards its side with a great

a
force as a result of which the shared pair of electrons will be displaced toward
hs
electronegative atom and away from a hydrogen atom.
at
Due to which hydrogen atom will acquire a slightly negative charge and if another molecule
lp

is brought nearer to it in such a way that electronegative atom of the second molecule
faces hydrogen atom of the 1st molecule, due to opposite charges present on the
ita

atoms, an electrostatic bond will be formed between the hydrogen atom of one
molecule and electronegative atom of 2nd molecule and this is called as hydrogen
ig

bond.
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w
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Conditions for hydrogen bonding. The following two necessary conditions for hydrogen
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bonding are:

1. Hydrogen atom should be connected to highly electronegative atom say F, O, or N.

2. The electronegative atom of which the hydrogen atom is connected should be the
same in size.

The smaller the size of the electronegative atom greater will be the attraction of that atom
for shared pair of electrons and hence that pair will be displaced more nearer to that
atom and hence that atom will develop greater negative charge and the hydrogen atom
will develop a greater positive charge and hence hydrogen atom of this molecule will
easily attract negative atom of the Ian molecule and hence a hydrogen bond will be

(36)
 STATES OF MATTER
05

easily formed.

As both these conditions are satisfied only by F, O, N atoms so only three atoms show
hydrogen bond.

Strength of Hydrogen Bond: A hydrogen bond is a very weak bond. It is weaker than an
ionic or a covalent bond. Its strength ranges from 13 kJ mol-1 to 42 kJ mol-1. The
strength of the hydrogen bond for some of the molecules is the order H-F H (40 kJ mol-
1) > O-H…… O (28 kJ mol-1) > H-N…… H (13 kJ mol-1) whereas the strength of a covalent
bond is quite high. For example, the bond strength of the H-H bond in H2 is 433 kJ mol-1

)
Types of H-bonding

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There are two types of hydrogen-bonds

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1. Intermolecular hydrogen bond. It is formed between two different molecules of the

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same or different compounds. For example H-bond in case of HF, alcohol, or water.

a
hs
2. Intramolecular Hydrogen bond. It is formed when a hydrogen atom is in between the
two highly electronegative (F, O, N) atoms present within the same molecule. For
at
example, in o-nitrophenol, hydrogen is in between the two oxygen atoms.
lp
ita
ig
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Assertion Reason Answer:

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1. (i) Both A and R are true and R is the correct explanation of A.

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2. (ii) Both A and R are true but R is not the correct explanation of A.

Case Study Answer:

1. Answer:

(1) (c) Less than unit electronic charge

(2) (b) Dispersion force

(3) (d) 1/r6

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 STATES OF MATTER
05

(4) (c) Ion-dipole forces

(5) (c) Br2

2. Answer:

(1) (b) H2O

(2) (d) Hydrogen chloride

(3) (a) Intermolecular hydrogen bonding

)
(4) (b) Intramolecular hydrogen bonds are formed between two different molecules of the

m
same compound.

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a la
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(38)
CHEMISTRY

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CHAPTER 6: THERMODYNAMICS

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 THERMODYNAMICS
06

THERMODYNAMICS
Introduction

Chemical thermodynamics deals with the relationship between various form of energy in a
process. Thermodynamics deals with macroscopic properties. This chapter introduces a major
subsidiary thermodynamic property, the Gibbs free energy which lets us express the spontaneity
of a process in terms of the properties of the system. This chapter helps to explain why gases
expand or diffuse.

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System and Surrounding

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1. System: A specific portion of universe under study which is seperated from rest of the
universe with a boundary is called system.

a la
2. Surroundings: Rest of the universe which might be in a position to exchange energy and
hs
matter with the system is known as surrounding.
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Types of System:
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1. Open system: System can be open if it can exchange both energy and matter with
ita

surroundings.

2. Closed system: System can be closed if it can exchange energy but not matter with
ig

surroundings.
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3. Isolated system: System can be isolated if it can neither exchange energy nor matter with
w

surroundings.
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Extensive Properties

The properties which depend upon mass of the substance is known as extensive properties i.e.,
mass, volume, internal energy, enthalpy etc.

Intensive Properties
The properties which are independent of mass of the substance is known as intensive properties
i.e., temperature, pressure, density, refractive index.

Thermodynamic State of a System

(1)
 THERMODYNAMICS
06

A state is the condition of a system as specified by its physical 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.

State Functions
The thermodynamic parameters which depends only on initial and final states of system is
known as state function. i.e., internal energy(E), Enthalpy (H), entropy (S), Gibb's free energy (G).

Path Functions

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The thermodynamic parameters where value does not depend merely on initial and final state
but depends upon the path followed is known as path function. i.e., heat (q), work done (W).

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Thermodynamic Process

a la
The sequence followed to change one thermodynamic state of a system into another is called
hs
thermodynamic process. The types of thermodynamic processes are:
1. Isothermal process: It is the process in which temperature is kept constant means
at
temperature of initial and final state of system along with entire path of process is same.
lp

2. Isobaric process: It is the process in which pressure is kept constant for entire process.
ita

3. Isochoric process: It is the process in which volume is kept constant.

4. Adiabatic process: The process in which heat transaction across boundary is not allowed.
ig

5. Reversible process and Irreversible process: In thermodynamics, a process is said to be

.d

reversible when energy change in each step of the process can be reversed by changing
w

the variables such as pressure, volume or temperature acting on them. In such a process,
w

the driving and opposing forces differ infinitesimally and the process can be reversed
completely by increasing the opposing force by an infinitesimally small amount.
(w

Any process which does not take place in the above mentioned manner is said to be an
irreversible process. In an irreversible process the driving and opposing force differ by a
large amount.
6. Cyclic process: It is the process which run in close loop means process in which initial and
final states are identical.

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 THERMODYNAMICS
06

)
m
Internal Energy

.co
Every substance is associated with definite amount of energy that is called internal energy. It is
an extensive property and a state function. Internal energy of ideal gases is a function of

la
temperature only.

a
Pressure-Volume Work hs
at
It is the work done when the gas expands or contracts against the external pressure. Consider a
lp

cylinder containing one mole of an ideal gas fitted with a frictionless and weightless piston
having an area of cross-section A. The total volume of the gas is Vi and the initial pressure of the
ita

gas inside P.
ig
.d
w
w
(w

Let the external pressure acting on the piston is Pex. If the external pressure Pex is slightly
greater than P piston moves downward till the pressure inside the cylinder becomes equal to
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 THERMODYNAMICS
06

Pex. Let this change be achieved in a single step and the final volume be Vf. During this
compression, suppose the piston moves a very small distance Δl. Thus, the work done on the gas
is given by,
Vf
ω = − ∫ Pex dv
Vi

Heat
The change in internal energy of a system can be brought about by the transfer of heat from the
surroundings to the system or vice-versa. This exchange of energy between the system and

)
surroundings is possible as a result of the temperature difference between them. This energy

m
called heat is represented by Q.

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First Law of Thermodynamics

la
First law of thermodynamics states the law of conservation of energy in a different manner.

a
According to this law, whenever a quantity of one kind of energy disappears an equivalent
amount of energy appears in some other form.
hs
at
According to first law of thermodynamics,
lp

ΔU = q + W
ita
ig

Where, Q = Heat change

.d

W = Work done
w
w

ΔU = Change in internal energy

(w

Enthalpy (H)
The total heat content of a system at constant pressure is known as its enthalpy. Mathematically
it is the sum of internal energy and pressure-volume energy

ΔH = ΔU + PΔV

It is an extensive property and a state function. Increase in enthalpy H is equal to heat absorbed
at constant pressure.

Heat Capacity
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 THERMODYNAMICS
06

Heat capacity is amount of heat require to raise the temperature of a system by unity. It is
represented as "C". It is an extensive property and temperature dependent.

Types of heat capacity

1. Specific heat: For 1 gram system the heat loose or gained by system to bring one unit
change in temperature is called specific heat denoted by 's'. specific heat is the intensive
property.
C
S=
m

)
2. Molar heat capacity: It is heat capacity for a system having 1 mole of material. It is

m
represented as Cm. It is an intensive property.

.co
C
Cm =
m

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3. Heat capacity at constant volume: Heat capacity of a system in isochoric condition is

a
hs
called heat capacity at constant volume, it is represented as Cv means molar heat
capacity at constant volume.
at
dU
lp

Cv =
dT
ita

4. Heat capacity at constant pressure: Heat capacity of a system in isobaric condition. It is

represented by Cp means molar heat capacity at constant pressure.
ig

dH
.d

Cp =
dT
w

Relation between Cp and Cv

w
(w

We know that,

ΔH = ΔU + PΔV .....(i)

As per ideal gas equation

PΔV = RΔT .....(ii)

From (i) and (ii)

ΔH = ΔU + RΔT

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 THERMODYNAMICS
06

∆H ∆U
= +R
∆T ∆T
Cp = Cv + R

Cp – Cv = R

Hess’s Law
According to Hess's law, If a reaction takes place in several steps then its standard reaction
enthalpy is the sum of the standard enthalpies of the intermediate reactions into which the

)
overall reaction may be divided at the same temperature.

m
1st method: C(s) + O2 (g) → CO2 (g) = ΔH

.co
1
2nd method: C(s) + O2 (g) → CO(g) = ΔH1

la
2

a
1
CO(s) + O2 (g) → CO2 (g) = ΔH2 hs
2
at
According to Hess's law,
lp

ΔH = ΔH1 + ΔH2
ita

Application of Hess's Law

ig

1. Calculation of enthalpy of formation.

.d

2. Determination of standard enthalpies of reactions.

w

Bond Dissociation Energy

w
(w

The energy required to break one mole bond of a particular type in gaseous molecule is known
as bond dissociation energy. For example, we consider the dissociation of water,

H − OH(g) → H(g) + OH(g) = ΔH = 498 kJ/mol

Entropy
Entropy is a measure of degree of randomness or disorder in a system. Entropy is an extensive
property and a state function.. Its value depends upon the amount of substance present in the
system.

Second Law of Thermodynamics

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 THERMODYNAMICS
06

This states that the entropy of the universe always increases in every spontaneous (natural)
change.

Free Energy (G)

Gibb's free energy is defined as,

ΔG = ΔH − TΔS

H is enthalpy, S is entropy and T is the temperature on Kelvin scale.

Measurement Of Change In Internal Energy and Enthalpy

)
m
The experimental technique of measuring energy changes accompanying any chemical or

.co
physical process is called calorimetry.

These measurements are generally carried out under 2 condition

a la
1) at constant volume ( ΔU or qv )

2) at constant pressure ( ΔH or qp)

hs
at
Measurements of ΔU
lp
ita
ig
.d
w
w
(w

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 THERMODYNAMICS
06

Internal energy change is measured experimentally using an apparatus called Bomb calorimeter.

It consists of a strong steel vessel which can stand high pressure. It is surrounded by a bigger
vessel which contains water and is insulated. A thermometer and a stirrer are suspended in it.

Procedure

1) A known mass of compound is taken in the platinum cup.Oxygen under high pressure is
introduced into the bomb. A current is passed through the filament immersed in the compound.
Combustion of the compound takes place. The increase in the temperature of water is noted.
From this, the heat capacity of the apparatus can be calculated.

)
2) The experiment is repeated as in step 1.As the reaction is carried out in a closed vessel,

m
therefore, heat evolved is the heat of combustion at constant volume and hence is equal to

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internal energy change.

la
The value of ΔU can be calculated using the formula

a
ΔU = (Q × Δt × M ) / m hs
where Q =heat capacity of the calorimeter
at
Δt = rise in temperature
lp
ita

m= mass of the substance taken

M =molecular mass of the substance

ig
.d

Measurement of ΔH
w
w
(w

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 THERMODYNAMICS
06

)
m
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a la
hs
Taking the example of heat of neutralisation of an acid with a base or vice versa, it can be
at
determined using a simple calorimeter consisting of a polythene bottle fitted with a cork having
lp

two holes , one for the thermometer and the other for the stirrer.
ita
ig
.d
w
w
(w

Instead of polythene bottle , a foamed polystyrene cup with a cover is also sometimes used .It is
called coffee cup calorimeter.
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 THERMODYNAMICS
06

Taking the example of neutralisation of HCl with NaOH.

1) A known volume of HCL of known concentration ( 100cm3 of 0.5 N ) is taken in one beaker
and an equal volume of NaOH of the same concentration (100cm3 of 0.5 N ) is taken in another
beaker.

2) Both the beakers are kept in water bath till the solution attain the same temperature.

3) HCl solution kept in the first beaker is transferred into the polythene bottle. Immediately
NaOH solution kept in the second beaker is added into the polythene bottle. Stirring is done to
mix HCl and NaOH. The highest temperature attained is noted.

)
Suppose the initial temperature of the acid and the base = t1 ° C

m
.co
Final temperature of the solution after mixing = t2 ° C

Rise in temperature= ( t2 – t1) °C

a la
Total mass of the solution = 200 g
hs
Heat produced = mass × specific heat × rise in temperature
at
Heat produced by neutralisation of 1000 cc of 1 N HCl
lp

This give the heat of neutralisation per equivalent.

ita

Heat of neutralisation of a strong acid by a strong base is always equal to 57.1 kJ equi-1 or 57.1
ig

kJ mol-1 of H+ or OH– ions.

.d

Measurement of ΔH or qp reaction for any reaction

w

For any reaction occurring in solution, the heat change accompanying the reaction at constant
w

pressure i.e. enthalpy change can be measured by using the calorimeter.

(w

The reaction is allowed to take place in the polythene bottle.

If the reaction is exothermic, temperature will rise and if the reaction is endothermic,
temperature will fall.

For exothermic reaction, ΔH is negative whereas for endothermic reaction, ΔH is positive.

For the measurement of qp or ΔH ,the reaction may be carried out in a vessel with conducting
walls.

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 THERMODYNAMICS
06

This vessel may be placed in an insulated outer vessel containing water and fitted with a stirrer
and a thermometer. The Rise or fall in temperature may be recorded and the result calculated.

Thermochemical Equation
When a balanced chemical equation not only indicates the quantities of the different reactants
and products but also indicates the amount of heat evolved or absorbed, it is called
thermochemical equation.

Fractional coefficients may be used in writing a thermochemical equation.

H2 ( g ) + ½ O2 ( g ) ———> H2O ( l ) + 285.8 KJ mol-1

)
m
H2 ( g ) + ½ O2 ( g ) ———> H2O ( l ) ΔH = – 285.8 KJ mol-1

.co
285.8 KJ mol-1 of heat is produced when 1 mole of hydrogen reacts with 0.5 mole of Oxygen. If
the quantities of reactants are doubled, the heat produced will also be doubled.

a la
2H2 ( g ) + O2 ( g ) ———> 2 H2O ( l ) + 571.6 KJ mol-1
hs
2H2 ( g ) + O2 ( g ) ———> 2H2O ( l ) ,ΔH = – 571.6 KJ mol-1
at
Conventions about thermochemical equation
lp

1)For exothermic reaction, ΔH is negative whereas for endothermic reaction, ΔH is positive.

ita

2)ΔH values are for the standard state of the substance ( 298 K and 1 bar pressure )
ig
.d

3) The coefficients of different substances represents the number of moles reacted and formed
for the heat change represented in the equation.
w
w

4) The physical state of the different substances must be mentioned as the heat evolved or
absorbed depends upon the physical state.
(w

5) If the coefficient of the substances are multiplied or divided by some number , the value of ΔH
is multiplied or divide by the same number.

6) If the reaction is reversed ,the sign of ΔH changes but the magnitude remains the same.

Heat of reaction or Enthalpy of reaction or Enthalpy change of reaction

The amount of heat evolved or absorbed in a chemical reaction when the number of moles of
reactants as represented by the chemical equation have completely reacted, is called the heat of
reaction or enthalpy of reaction or enthalpy change of reaction.

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 THERMODYNAMICS
06

It is represented by Δr H.

For example

CH4 ( g ) + O2 ( g ) ————> CO2 ( g ) + 2 H2O ( l ) ΔH = – 890.4 KJ mol-1

C ( s ) + H2O ( g ) ———> CO ( g ) + H2 ( g ) ΔH = 131 Kj mol-1

1 mole of methane combines completely with 2 moles of Oxygen gas, 890.4 KJ of heat is
produced.

1 mole of solid carbon react completely with one mole of steam ,131.4 KJ of heat is absorbed.

)
m
Enthalpy of reaction, ΔH = Sum of enthalpies of products – Sum of enthalpies of reactants

.co
ΔH = ∑ai H (products) – ∑bi H (reactants)

la
where symbol ∑ represent summation, ai and bi represents the coefficient of the products and
reactants.

a
hs
If the reaction is reversed , the sign of ΔH changes
at
H2 ( g ) + ½ O2 ( g ) ———> H2O ( l ) ΔH = – 285.8 KJ mol-1
lp

H2O ( l ) ——–>H2 ( g ) + ½ O2 ( g ) ΔH = 285.8 KJ mol-1

ita

Factors on which the heat of reaction depends

ig

1) Quantities of the reactants involved

.d

If the quantities of reactants are doubled, the heat of reaction is also doubled.
w
w

2)Physical state of the reactants and products

(w

The physical state of the reactants and products affects the heat of reaction.

When hydrogen and oxygen gas combine to form liquid water, the heat of reaction is different
than when they combine to form water in the gaseous state.

H2 ( g ) + ½ O2 ( g ) ———> H2O ( l ) ΔH = – 285.8 KJ mol-1

H2 ( g ) + ½ O2 ( g ) ———> H2O ( g ) ΔH = – 241.8 KJ mol-1

It is essential to write the symbols s, l, g or aq to indicate whether a particular substance is a

solid ,liquid ,gaseous or an aqueous solution.

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 THERMODYNAMICS
06

3)Allotropic modification

For elements like Sulphur and carbon which exist in different allotropic modification, the heat of
reaction is different in different allotropic form is involved in the reaction.

C ( diamond ) + O2 ( g ) ——–> CO2 ( g) , ΔH = -395.4 KJ mol-1

C ( graphite ) + O2 ( g ) ——–> CO2 ( g) , ΔH = -395.4 KJ mol-1

4)Concentration of solution

Heat changes occurs when a solute is dissolved in a solvent to form a solution or when solution is

)
diluted.

m
Therefore, if the solutions are involved in a reaction, their concentration affect the heat of

.co
reaction.

la
5)Temperature

a
hs
The heat of reaction depends upon the temperature at which the reactants and products are
taken. The values are usually reported at 298 K.
at
6)Conditions of constant pressure or constant volume
lp

Whether the reaction take place at constant pressure or at constant volume.

ita

Standard enthalpy of reaction

ig

The enthalpy change of a reaction depends upon the condition under which the reaction is
.d

carried out. Hence it is essential to specify some standard conditions.

w

The standard enthalpy of a reaction is the enthalpy change accompanying the reaction when all
w

the reactants and products are taken in their standard state.

(w

A substance is said to be in standard state when it is in the purest and most stable form at 1 bar
pressure and the specified temperature.

This temperature is usually taken as to 298 K.

Standard state of pure ethanol at 298 k is pure liquid ethanol at 298 K and 1 bar pressure.

in terms of S.I. unit, 1 atm=101.325 KPa whereas 1 bar = 105 Pa .

The enthalpy change of a reaction in the standard state is represented by the symbol ΔH°

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 THERMODYNAMICS
06

Bond Enthalpy
Bond energy is the amount of energy released when 1 mole of bonds are formed from the
isolated atoms in the gaseous state or the amount of energy required to dissociate one mole of
bonds present between the atoms in the gaseous molecules.

It is represented by Δ b H or Δbond H.

For diatomic molecules like H2, O2, N2, Cl2, HCl, HF etc. the bond energies are equal to their
dissociation energies. These may also be called as their enthalpy of atomisation.

For polyatomic molecules ,the bond energy of a particular bond is not the same when present in

)
m
different types of compounds.

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The bond energy of a particular type of bond is not same even in the same compound.

For Ex: In CH4 the bond energy for first, second ,third and fourth C-H bonds are not equal: their

la
values being 427, 439, 452 and 347 KJ mol-1

a
ΔaH° = 427 + 439 + 452 + 347
hs
at
ΔaH° = 1665 KJ mol-1
lp

To calculate bond energy, an average is taken.

ita

ΔC-H = 1665 / 4 = 416 KJ mol-1

ig

Bond energy usually means bond dissociation energy. It is always taken as positive because it is
.d

the energy required and not the energy released. It is the energy for one mole of a particular
type of bonds and not for 1 mole of the substance.
w
w

Bond dissociation energies are obtained at 0 K by spectroscopic method whereas bond enthalpy
are calculated by considering combustions from heat capacities and pΔV terms.
(w

Bond enthalpy helps to calculate the enthalpy of formation of atoms.

For polyatomic molecules ,the bond enthalpy of a particular bond is found from the values of the
enthalpies of formation.

Bond enthalpy of heteronuclear diatomic molecules can be obtained directly from the
experiments or may be calculated from the bond enthalpies of homonuclear diatomic molecules.

Spontaneous and Non-spontaneous Process

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 THERMODYNAMICS
06

A process which under some conditions may take place by itself or by initiation independent of
the rate is called spontaneous process.

A process which can take place by itself or has an urge or tendency to take place is called
spontaneous process.

A spontaneous process is simply a process which is feasible.

The rate of the process may vary from extremely slow to extremely fast.

Examples of processes which take place by themselves :

)
1) Dissolution of common salt in water

m
2) Evaporation of water in an open vessel

.co
3) Flow of heat from hot end to cold end or from a hot body to a cold body

la
4) Flow of water down a hill

a
hs
5) Combination of nitric oxide and oxygen to form Nitrogen dioxide
at
2NO ( g ) + O2 ( g ) ———–> 2NO2 ( g )
lp

Examples of processes which take place on initiation

ita

1) Lightning of candle involving burning of wax

ig

2) Heating of calcium carbonates to give calcium oxide and carbon dioxide

.d

CaCO3 ( s ) ————–> CaO ( s ) + CO2 ( g )

w
w

3) Combination of hydrogen and oxygen to form water when initiated by passing an electric
spark
(w

H2 ( g ) + ½ O2 ( g ) ———> H2O ( g )

A process which can neither take place by itself nor by initiation is called a non spontaneous
process.

For Example

1) Flow of water up a hill

2) Flow of heat from cold body to a hot body

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 THERMODYNAMICS
06

3) Diffusion of gas from low pressure to a high pressure

4) Dissolution of sand in water

The force which is responsible for the spontaneity of a process is called a driving force

Nature of driving force

In order to acquire maximum stability, every system tends to have minimum energy.

Tendency for minimum energy

)
For example

m
1) A stone lying at height has a tendency to fall down so as to have minimum potential energy

.co
2) Water flows down a hill to have minimum energy

la
3) A wound watch spring has tendency to unbind itself to decrease its energy to minimum

a
hs
4) Heat flows from hot body to cold body so that heat content of the hot body becomes
minimum
at
All the processes are spontaneous because they have tendency to acquire minimum energy.
lp
ita

Consider the following exothermic reaction, all of which are spontaneous :

1) H2 ( g ) + ½ O2 ( g ) ———–> H2O ( l ) ΔrH° = -285.8 KJ mol-1

ig
.d

2) N2 ( g ) + 3H2 ( g ) ———–> 2NH3 (g) ΔrH° = -92.2 KJ mol-1

w

3)C ( s ) + O2 ( g ) ————> CO2 ( g ) ΔrH° = -285.8 KJ mol-1

w

All these reactions are accompanied by evolution of heat. The heat content of the products is
(w

less than those of the reactants. These reactions are spontaneous because they are
accompanied by decrease of energy.

A tendency to attain minimum energy i.e. a negative value of enthalpy change, might be
responsible for a process or a reaction to be spontaneous or feasible.

limitation of the criteria for minimum energy

1) A number of reactions are known which are endothermic i.e. for which ΔH is positive but still
they are spontaneous.

1) Evaporation of water or melting of ice

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 THERMODYNAMICS
06

It takes place by absorption of heat from the surrounding.

H2O ( l ) ———-> H2O ( g ) Δvap H° = 40.8 KJ mol-1

H2O ( s ) ———-> H2O ( l ) Δfus H° = 6 KJ mol-1

2) Dissolution of salts like NH4Cl , KCl

NH4Cl (s) + aq ——–> NH4 + (aq) + Cl – (aq ) ΔrH° = 15.1 KJ mol-1

3) Decomposition of calcium carbonate on heating

CaCO3 ( s ) ————> CaO (s ) + CO2 ( g ) ΔrH° = 177.8 KJ mol-1

)
m
4) Decomposition of N2O5 at room temperature

.co
2N2O5 ( g ) ———–> 4NO2 ( g ) + O2 ( g ) ΔrH° = 219 KJ mol-1

la
5) Decomposition of mercuric oxide on heating

a
hs
2HgO ( s ) ———–> 2Hg ( l ) + O2 ( g ) ΔrH° = 90.8 KJ mol-1
at
2) A number of reactions are known for which ΔH is zero but still they are spontaneous
lp

Reaction between acetic acid and ethyl alcohol

ita

CH3COOH ( l ) + C2H5OH ( l ) ———> CH3COOC2H5 ( l ) + H2O ( l )

ig

2) Expansion of an ideal gas into vacuum

.d

3) Even those reactions for which ΔH is negative, rarely proceed to completion even though ΔH
w

remains negative throughout.

w

4) Reversible reactions also occur.

(w

H2 ( g ) + I2 ( g ) ——>2HI (g )

2HI (g ) ———-> H2 ( g ) + I2 ( g )

The energy factor or enthalpy factor cannot be the sole criterion for predicting the spontaneity
or the feasibility of a process.

Tendency for maximum randomness

Suppose the two gases are enclosed in bulbs A and B connected to each other by a tube and kept
separated by a stopcock. If the stock cock is opened the two gases mix completely. The gases
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 THERMODYNAMICS
06

which were confined to bulbs A and B separately are no longer in order. A disorder has come in
or the randomness of the system has increased.

A spontaneous process for which ΔH = 0 is the spreading of a drop of ink in a beaker filled with
water.

Second factor which is responsible for the spontaneity of a process is the tendency to acquire
maximum randomness.

For example:

1) Evaporation of water take place because the gaseous water molecules are more random than

)
the liquid water molecules. The process is spontaneous because it is accompanied by increase of

m
randomness. Melting of ice is a spontaneous process because liquid state is more random than

.co
the solid state.

la
2) Dissolution of Ammonium Chloride is spontaneous because in the solid, the ions are fixed but
when they go into the aqueous solution, they are free to move about.

a
hs
3) Decomposition of solid calcium carbonate is spontaneous because CO 2 produced is more
random than the solid CaCO3.
at
lp

4) Decomposition of N2O5 is spontaneous because 2 moles of gaseous N2O5 give 5 moles of

gaseous product .
ita

5) Decomposition of solid Mercury oxide is spontaneous because the liquid Mercury and gaseous
ig

oxygen formed are more random than solid HgO.

.d

The overall tendency for a process to occur depends upon the resultant of the following two
w

tendencies :
w

1) Tendency for minimum energy

(w

2) Tendency for maximum randomness

The resultant of the above 2 tendencies which gives the overall tendency for a process to occur
is called the driving force of the process.

For example :

E represents the tendency for minimum energy

R represents the tendency for maximum randomness.

D represent the overall tendency

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 THERMODYNAMICS
06

1) Evaporation of water

H20 ( l ) ———-> H2O ( g ) ΔH = 44 kJ mol-1

E opposes( process being endothermic), R favours (because gas is more random than
liquid).Since the process is known to be spontaneous hence R must be greater than E.

2)Dissolution of NH4Cl in water

NH4Cl ( s ) + aq ————> NH4+ (aq ) + Cl – (aq) ΔH = 15.1 kJ mol-1

In this process E opposes and R favour. Here again , the spontaneity of the process is explained

)
by suggesting that R > E.

m
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Summary

a la
1. System: A part of universe which is under investigation.
hs
2. Surroundings: The rest of the universe which is not a part of the system.
at
3. State of the system: The conditions of existence of a system when its macroscopic
lp

properties have definite values.

ita

4. State functions: The thermodynamic quantities which depend only on the initial and final
state of the system.
ig
.d

5. Energy: Energy is exchanged between the system and the surroundings as heat if they
are at different temperatures.
w
w

6. The properties of the system whose value is independent of the amount of substance are
called intensive properties. e.g., temperature, pressure, viscosity, surface tension,
(w

dielectric constant, specific heat capacity.

7. The properties of the system whose value depends upon the amount of substance
present in the system are called extensive properties. e.g., mass, volume, surface area,
energy, enthalpy, entropy, free energy, heat capacity.

8. Work is also a mode of transference of energy between system and the surroundings.
Work done by the system on the surroundings is given by pΔV.

9. Internal energy (U): The energy associated with the system at a particular conditions of
temperature and pressure.

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 THERMODYNAMICS
06

10.Enthalpy (H): It is sum of internal energy and pressure-volume energy of the system at a
particular temperature and pressure. It is also called heat content (H = E + pV).

11.Hess’s law: The enthalpy change in a particular reaction is the same whether the reaction
takes place in one step or in a number of steps.

12.Bond enthalpy: The average amount of energy required to break one mole of the bonds
of a particular type in gaseous molecules.

13.Entropy (S): It is a measure of randomness or disorder of the system. Thus, the order is
Gas > Liquid > Solid.

)
m
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a la
hs
at
lp
ita
ig
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(20)
 06

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THERMODYNAMICS

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w
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ig
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hs
ala
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 THERMODYNAMICS
06

Important Questions
Multiple Choice questions-
Question 1. Hesss law is an application of
(a) 1st law of Thermodynamics
(b) 2nd law of Thermodynamics
(c) Entropy change
(d) ∆H = ∆U + P∆V.
Question 2. 5 mole of an ideal gas expand isothermally and irreversibly from a pressure of 10

)
m
atm to 1 atm against a constant external pressure of 1 atm. Wirr at 300 K is:

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(a) -15.921 kJ
(b) -11.224 kJ

la
(c) -110.83 kJ

a
(d) None of these hs
Question 3. At absolute zero the entropy of a perfect crystal is zero. This statement
at
corresponds to which law of thermodynamics?
lp

(a) Zeroth Law

ita

(b) First Law

(c) Second Law
ig

(d) Third Law

.d

Question 4. Which of the following has the highest entropy?

w

(a) Mercury
w

(b) Hydrogen
(w

(c) Water
(d) Graphite
Question 5. An ideal gas is taken through the cycle A → B → C → A as shown in figure. If the net
heat supplied to the gas in cycle is 5 J, the work done by the gas in the process C → A.

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 THERMODYNAMICS
06

(a) -5 J

)
m
(b) -15 J

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(c) -10 J
(d) -20 J

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Question 6. One mole of which of the following has the highest entropy?

a
(a) Liquid Nitrogen hs
(b) Hydrogen Gas
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(c) Mercury
lp

(d) Diamond
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Question 7. An ideal gas is taken around the cycle ABCA as shown in P-V diagram The next work
done by the gas during the cycle is equal to:
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w
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(a) 12P1V1
(b) 6P1V1
(c) 5P1V1
(d) P1V1
Question 8. Third law of thermodynamics provides a method to evaluate which property?

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 THERMODYNAMICS
06

(a) Absolute Energy

(b) Absolute Enthalpy
(c) Absolute Entropy
(d) Absolute Free Energy
Question 9. Which of the following is/are a reason that water is a desirable heat sink for use in
calorimeters?
I) Waters heat specific capacity is very precisely known.
II) Water is readily available.

)
III) Water has an unusually large specific heat capacity.

m
(a) I only

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(b) I and II

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(c) I, II and III

a
(d) II only
hs
Question 10. In a chemical reaction the bond energy of reactants is more than the bond energy
of the products. Therefore, the reaction is
at
(a) Exothermic
lp

(b) Athermic
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(c) Endothermic
ig

(d) Endergonic
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Question 11. In a reversible process the system absorbs 600 kJ heat and performs 250 kJ work
w

on the surroundings. What is the increase in the internal energy of the system?
w

(a) 850 kJ
(w

(b) 600 kJ
(c) 350 kJ
(d) 250 kJ
Question 12. Which of the following neutralization reactions is most exothermic?
(a) HCl and NaOH
(b) HCN and NaOH
(c) HCl and NH4OH
(d) CH3COOH and NH4OH

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 THERMODYNAMICS
06

Question 13. A student runs a reaction in a closed system. In the course of the reaction, 64.7 kJ
of heat is released to the surroundings and 14.3 kJ of work is done on the system. What is the
change in internal energy (∆U) of the reaction?
(a) -79.0 kJ
(b) 50.4 kJ
(c) 79.0 kJ
(d) -50.4 kJ
Question 14. Identify the correct statement from the following in a chemical reaction.
(a) The entropy always increases

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(b) The change in entropy along with suitable change in enthalpy decides the fate of a reaction

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(c) The enthalpy always decreases
(d) Both the enthalpy and the entropy remain constant

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Question 15. 2 mole of an ideal gas at 27° C expands isothermally and reversibly from a volume

a
of 4 litters to 40 litre. The work done (in kJ) is:
hs
(a) w = -28.72 kJ
at
(b) w = -11.488 kJ
lp

(c) w = -5.736 kJ
ita

(d) w = -4.988 kJ
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Very Short:
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1. Under what conditions the heat evolved or absorbed is equal to the internal energy
w

change?
w

2. What is the sign of AH for endothermic reactions and why?

(w

3. What is the relationship between the standard enthalpy of formation and the enthalpy of
a compound?
4. Why enthalpy of neutralization of HF is greater than 57.1 kJ mol-1?
5. What are the specific heat capacity and molar heat capacity for water?
6. Why enthalpy of neutralization is less if either the acid or the base or both are weak?
7. What do you mean by a system?

Short Questions:
1. Ice is lighter than water, but the entropy of ice is less than that of water. Explain.
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 THERMODYNAMICS
06

2. Define spontaneity or-feasibility of a process.

3. Enthalpy of neutralization of CH3COOH and NaOH is 55.9 kJ. What is the value of ΔH for
ionization of CH3COOH?
4. When 1 gm of liquid naphthalene (C10H8) solidifies, 150 J of heat is evolved. What is the
enthalpy of fusion of C10H8?
5. Why most of the exothermic processes (reactions) are spontaneous?
6. What is meant by the term state function? Give examples.

Long Questions:

)
m
1. Define

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(i) Standard enthalpy of formation.
(ii) Standard enthalpy of combustion

la
(iii) Enthalpy of atomization

a
(iv) Enthalpy of solution hs
(v) Lattice enthalpy
at
(vi) Thermochemical equation.
lp

2. For the equilibrium PCl5(g) ⇌ PCl3(g) + Cl2(g) at 298 K, Kc = 1.8 × 10-7. What is ΔG° for the
reaction? (R = 8.314 JK-1 mol-1).
ita

3. Calculate the equilibrium constant, K, for the following reaction at 400 K?

ig

2NOCl(g) ⇌ 2NO(g) + Cl2(g)

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Given that ΔrH° = 80.0 kJ mol-1 and ΔrS° = 120 JK-1 mol-1.
w

4. Calculate the standard entropy change for the reaction X ⇌ Y if the value of ΔH° = 28.40 kJ
w

and equilibrium constant is 1.8 × 10-7 at 298 K and ΔrG° = 38.484 kJ.
(w

Assertion Reason Questions:

1. In the following questions, a statement of Assertion (A) followed by a statement of Reason
(R) is given. Choose the correct option out of the choices given below each question.

Assertion (A): Combustion of all organic compounds is an exothermic

reaction.
Reason (R) : The enthalpies of all elements in their standard state are zero.
(i) Both A and R are true and R is the correct explanation of A.

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 THERMODYNAMICS
06

(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A is false but R is true

2. In the following questions, a statement of Assertion (A) followed by a statement of Reason

(R) is given. Choose the correct option out of the choices given below each question.

Assertion (A) : Spontaneous process is an irreversible process and may be

reversed by some external agency.
Reason (R) : Decrease in enthalpy is a contributory factor for spontaneity.

)
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(i) Both A and R are true and R is the correct explanation of A.

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(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.

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(iv) A is false but R is true.

a
Case Study Based Question: hs
1. This law was presented by Hess in 1840. According to the law, if a chemical reaction can be
at
made to take place in a number of ways in one or in several steps, the total enthalpy change
lp

is always the same.

ita

Thus, the total enthalpy change of a chemical reaction depends on the initial and final stages
only.
ig
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(27)
 THERMODYNAMICS
06

)
m
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a la
hs
at
lp
ita
ig

(1) In which of the enlisted cases, Hess’s law is not applicable?

.d

(a) Determination of lattice energy

w

(b) Determination of resonance energy

w

(c) Determination of enthalpy of transformation of one allotropic form to another

(w

(d) Determination of entropy

(2) Use the bond energy data and calculate the enthalpy change for

The Bond energies of C ꟷ H and C ꟷ CI are 413 and 328 kJ mol-1 respectively.
(a) – 1465 kJ/mol
(b) 1465 kJ/mol

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 THERMODYNAMICS
06

(c) – 1482 kJ/mol

(d) 1482 kJ/mol
(3) A hypothetical reaction, A 2B, proceeds through the following sequence of steps:

The heat of reaction is

(a) q1 – q2 + 2q3

)
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(b) q1 + q2 - 2q3

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(c) q1 + q2 + 2q3
(d) q1 – 2q2 + 2q3

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2. The enthalpy of a system is defined as the sum of the internal energy of the system and the

a
energy that arises due to its pressure and volume. Mathematically, the enthalpy is defined
by the equation,
hs
at
H = U + PV
lp

Enthalpy change (ΔH) of a system is the heat absorbed or evolved by the system at constant
pressure.
ita

ΔH = qp, ΔH = ΔU + PΔV
ig

(1) Which of the following is not correct about enthalpy?

.d

(a) It is an extensive property

w

(b) It is not a state function

w

(c) Its absolute value cannot be determined

(w

(d) Enthalpy of a compound is equal to the enthalpy of formation of that compound.

(2) Lattice enthalpies are determined by:

(a) Born-Haber cycle
(b) Hess’s law
(c) lattice cycle
(d) None of these

(3) In which of the following thermochemical changes ΔH is always negative?

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 THERMODYNAMICS
06

(a) Enthalpy of solution

(b) Enthalpy of hydrogenation
(c) Enthalpy of reaction
(d) Enthalpy of transition

Answer Key:
MCQ
1. (d) 1st law of Thermodynamics

)
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2. (b) -11.224 kJ

.co
3. (d) Third Law

la
4. (b) Hydrogen

a
5. (a) -5 J hs
at
6. (b) Hydrogen Gas
lp

7. (c) 5P1V1
ita

8. (c) Absolute Entropy

ig

9. (c) I, II and III

.d

10.(c) Endothermic
w

11.(c) 350 kJ
w
(w

12.(a) HCl and NaOH

13.(d) -50.4 kJ

14.(b) The change in entropy along with suitable change in enthalpy decides the fate of a
reaction

15.(b) w = -11.488 k

Very Short Answer:

1. At constant volume.
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 THERMODYNAMICS
06

2. AH is positive as ΔH = Hp - Hr and Hr < Hp.

3. They are equal.

4. This is due to the high hydration energy of fluoride ions.

5. Specific heat capacity for H2O = 4.18 JK-1 g-1

Molar heat capacity for H2O = 4.18 × 18 = 75.24 JK-1 mol-1.

6. A part of the heat is used up for dissociation of the weak acid or weak base or both

)
7. A specified part of the universe that is under thermodynamic observation is called a system.

m
.co
Short Answer:

la
Ans: 1. Water is the liquid form while ice is its solid form. Molecular motion in ice is restricted

a
than in water, i.e., a disorder in ice is restricted than water, i.e., a disorder in ice is less than in
water. hs
at
Ans: 2. Spontaneity or feasibility of a process means its inherent tendency to occur on its own
lp

in a particular direction under a given set of conditions.

ita

Ans: 3. The heat of neutralization of strong acid and strong base + ΔH of ionization of CH3COOH
= Enthalpy of neutralization of CH3COOH and NaOH
ig

∴ – 57.1 kJ + ΔH of ionization of CH3COOH = – 55.9 kJ

.d

∴ ΔH of ionization of CH3COOH = (- 55.9 + 57.1) kJ

w

= 1.2 kJ.
w

Ans: 4. ΔHsolidifcation = – 150 × 128 = – 19200 J = – 19.2 kJ

(w

[∵ M.wt.of C10H8 = 128]

Ans: 5. ΔG = ΔH – TΔS; For exothermic reactions,

ΔH is -ve For a spontaneous process ΔG is to be -ve.

Thus decrease in enthalpy (- AH) contributes significantly to the driving force (To make ΔG
negative).

Ans: 6. A state function is a thermodynamic property that depends upon the state of the
system and is independent of the path followed to bring about the change. Internal energy
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 THERMODYNAMICS
06

change (ΔU), enthalpy change (ΔH) entropy change (ΔS), and free energy change (ΔG) are
examples.

Long Answer:
Ans: 1. Standard enthalpy of formation: The heat change accompanying the formation of 1 mole
df a substance from its elements in their most stable state of aggregation is called its standard
enthalpy of formation.
1
H2(g) + O2(g) H2O(l); Δf He = 285.8 kJ mol-1
2

)
m
(ii) Standard enthalpy of combustion: It is the heat change accompanying the complete
combustion or burning of one mole of a substance in its standard state in excess of air or

.co
oxygen.

la
13
C4H10(g) + O2(g) → 4CO2(g) + 5H2O(1); ΔHθ = – 2658.0 kJ mol-1.
2

a
hs
(iii) Enthalpy of atomization: It is defined as the enthalpy change accompanying the breaking of
one mole of a substance completely into its atoms in the gas phase.
at
H2(g) → 2H(g) ΔcHe = 435.0 kJ mol-1
lp
ita

(iv) Enthalpy of solution: It is defined as the heat change when one mole of a substance dissolves
in a specified amount of the solvent. The enthalpy of solution at infinite dilution is the
ig

enthalpy change observed on dissolving 2 moles of the substance in an infinite amount of the
.d

solvent.
w

(v) Lattice Enthalpy: The lattice enthalpy of an ionic compound is the enthalpy change that occurs
w

when one mole of an ionic compound dissociates into its ions in a gaseous state.
(w

(vi) Thermochemical Equation: A balanced chemical equation together with the value of its A^H is
called a thermochemical equation.

The above equation describes the combustion of liquid ethanol. The negative sign indicates that
tills are an exothermic reaction. We specify the physical state along with the allotropic state of
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 THERMODYNAMICS
06

the substance in a thermochemical equation.

Ans: 2.

)
Ans: 3.

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a la
hs
at
Ans: 4.
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= -33.8 JK-1 mol-1

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Assertion Reason Answer:

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1. (ii) Both A and R are true but R is not the correct explanation of A.

2. (ii) Both A and R are true but R is not the correct explanation of A.

Case Study Answer:

1. Answer:

(1) (d) Determination of entropy

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 THERMODYNAMICS
06

(2) (c) – 1482 kJ/mol

(3) (c) q1 + q2 + 2q3

2. Answer:

(1) (b) It is not a state function

(2) (a) Born-Haber cycle
(3) (b) Enthalpy of hydrogenation

)
m
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laa
hs
at
lp
ita
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(34)
CHEMISTRY

)
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CHAPTER 7: EQUILIBRIUM

a la
hs
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 EQUILIBRIUM
07

EQUILIBRIUM
Introduction

Equilibrium is the most important characteristic property of reversible reactions. These

reactions for which the forward reaction occurs to a much greater extent are considered to be
unidirectional in nature and whenever the rate of forward reaction is equal to rate of
backward reaction, equilibrium is attained, not to forget that equilibrium exists only in closed
system.
It is the state of system at which temperature, pressure, volume and composition have fixed
value and does not vary with time. Chemical Reactions can be divided into two categories:

)
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Irreversible Reactions: The reactions which proceed to completion and the products fail to
recombine to give back reactants. For example:

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AgNO3 + NaCl → AgCl + NaNO3

la
Reversible Reactions: The reactions which never go to completion and products recombine to
sa
give back reactants. For example:
th
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
a
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N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

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Physical Equilibrium
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i
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We know that solid, liquid and gas are the three states of substance. Therefore, three types of
w

physical equilibrium are possible. These are

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Solid(s) ⇌ liquid (l)

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Liquid(l) ⇌ gas(g)

Solid(s) ⇌ gas(g)

Here the sign double half arrows (⇌) pointing in the opposite directions is both for the
reversible change as well as for the equilibrium state.

1. Solid(s) – liquid(l) equilibrium: At equilibrium two processes takes place at the same
rate i.e.,

Ice(s) ⇌ water(l)

H2O(s) ⇌ H2O(l)

At equilibrium,

(1)
 EQUILIBRIUM
07

Rate of melting of ice = Rate of freezing of water

The temperature at which the solid and liquid states of a pure substance are in
equilibrium at the atmospheric.

pressure is called the normal freezing point or melting point of that substance.

2. Liquid(l) – gas(g) equilibrium:

H2O(l) ⇌ H2O(g)

In such type of equilibrium,

Rate of vaporisation of water = Rate of condensation of water vapour

)
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3. Solid(s) – gas(g) equilibrium: Such type of equilibrium is attained in case of volatile
solids.

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Example: If solid iodine is placed in a closed vessel, violet vapours starts appearing in

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the vessel.
sa
The intensity of violet vapour increases with time and ultimately it becomes constant.
th
I2(s) ⇌ I2(g)
a
lp

In this equilibrium,
ta

Rate of sublimation = Rate of condensation

gi

4. Solids in liquids: Suppose sugar is added continuously into a fixed volume of water at
i
.d

room temperature and stirred thoroughly with a glass rod. First the sugar will keep on
dissolving but then a stage will come when no more sugar dissolves. Instead it settles
w

down at the bottom. The solution is now said to be saturated and in a state of
w

equilibrium. In this state

(w

Rate of dissolution = Rate of precipitation

Sugar(s) ⇌ Sugar (in solution)

(2)
 EQUILIBRIUM
07

The amount of the solid in grams that dissolves in 100 g of the solvent to form a
saturated solution at a particular temperature is called the solubility of that solid in
the given solvent at that temperature.

Gases in liquids

Such type of equilibrium is present in soda water bottle in which CO2 gas is dissolved in water
under high pressure. There is a state of dynamic equilibrium between the CO 2 present in the
solution and the vapours of the gas above the liquid surface at a given temperature.

CO2(g) ⇌ CO2(aq)

)
Law Of Mass Action

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Law Of Mass Action

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la
The rate at which a substance reacts is proportional to its active mass and hence the rate of a
chemical reaction is proportional to the product of the active masses of the reactants.
sa
th
The active mass means molar concentration i.e. number of moles dissolved per litre of the
solution.
a
lp

Suppose x g of NaOH are dissolved in V litres of solution.Then we can say:

ta
gi

Concentration of NaOH solution = x g in V litre = x/40 moles in V litres = x / 40 × V moles/Litre

i
.d

Consider the reaction

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A + B ————-> products
w
(w

According to Law of mass action,

Rate at which A reacts ∝ [A]

Rate at which B reacts ∝ [B]

Rate at which A and B react together ∝ [A] [B] = K [A] [B]

where K is a constant of proportionality and is called velocity constant.

aA + bB → products

rate ∝ [A]m [B]n

(3)
 EQUILIBRIUM
07

The rate of a reaction is proportional to the product of the active masses of the reactants ,
each raised to the power equal to its stoichiometric coefficient as represented by the
balanced chemical equation.

Henry’s law
Periodic table may be defined as the tabular arrangement of elements in such a way that the
elements having same properties are kept together.

m ∝p

m = kp

where k is Henry’s constant and its value depends upon the nature of the gas, nature of liquid

)
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and temperature.

General Characteristics of Physical Equilibrium:

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1. Equilibrium is possible only in a closed system at a given temperature.
2. Both the opposing processes occur at the same rate and there is a dynamic but stable
sa
condition.
th
3. All measurable properties of the system remain constant.
4. When equilibrium is attained for a physical process, it is characterised by constant
a
lp

value of one of its parameters at a given temperature.

5. The magnitude of such quantities at any stage indicates the extent to which the
ta

physical process has proceeded before reaching equilibrium.

gi

Chemical Equilibrium
i
.d

Every reversible reaction consists of one pair of reaction, one is forward and other is
w

backward reaction. At one stage during reversible reactions, forward and backward reaction
w

proceed at the same time with the same rate, the reaction is then said to be in equilibrium.
If the opposing processes involve chemical reactions, the equilibrium is called Chemical
(w

equilibrium.

1. Law of Chemical Equilibrium: This law states that the rate of an elementary reaction
is proportional to the product of the concentration of the reactants. At a constant
temperature, the rate of a chemical reaction is directly proportional to the product of
the molar concentrations of the reactants each raised to a power equal to the
corresponding stoichiometric coefficients as represented by the balanced chemical
equation. Let us consider the reaction,

A+B⇌C+D

rf = Kf[A][B]

rb = Kb[C][D]

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 EQUILIBRIUM
07

At equilibrium rf = rb.

Kf[A][B] = Kb[C][D]
K c [C][D]
Kc = =
K c [A][B]

Kc is called the equilibrium constant, [ ] ⟶ denotes active masses.

For a general reversible reaction,

aA + bB ⇌ cC+ dD

[C]c [D]d

)
Kc =
[A]A [B]B

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2. Equilibrium constant of reverse reaction: Equilibrium constant for the reverse

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reaction is the inverse of the equilibrium constant for the reaction in the forward

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direction.
1
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K ′c =
Kc
a th

Relation between Kp and Kc

lp

For a general reversible reaction

ta

aA + bB ⇌ cC+ dD
i gi

[CC ]C [CD ]d
.d

Kc = … (1)
[CA ]a [CB ]b
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[PC ]C [PD ]d
w

Kp =
[PA ]a [PB ]b
(w

[CC ]C × [RT]C . [CD ]d × [RT]d

Kp =
[CA ]a × [RT]a . [CB ]b × [RT]b

[CC ]C [CD ]d (RT)c+b

Kp =
[CA ]a [CB ]b (RT)a+b
From Eq. (1),

K p = K C (RT)(c+d)−(a+b)

K p = K c (RT)Δn

Where, Δn = difference of stoichiometric coefficients of gaseous products and reactants.

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 EQUILIBRIUM
07

3. Characteristics of Equilibrium

i. At the state of equilibrium, certain available properties like pressure, concentration and
density becomes constant.

ii. Chemical equilibrium can be established from either side.

iii. A catalyst can cause the state of equilibrium to be reached faster, but does not alter the
state of equilibrium.

iv. Chemical equilibrium is dynamic in nature.

v. Any change in external stress (Pressure, temperature or concentration) causes

disturbance in equilibrium state. The state of equilibrium being stable, is again reached

)
by some adjustment.

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vi. If temperature is changed, a new equilibrium is achieved with a new value for relative

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concentration of products and reactants.

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vii. If temperature is kept constant, pressure and concentration of reactants / products is
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altered, system shifts in forward or backward direction in order to nullify the alteration
th
(stress).
a

Factors Affecting Equilibria

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i. Change in Concentration: When the concentration of any of the reactants or products in an

ta

equilibrium reaction is altered, the equilibrium mixture’s composition changes in order to

gi

minimize the effect of the concentration change.

i
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ii. Change in Temperature: According to Le-Chatelier’s principle if the temperature of an

equilibrium system is increased, the equilibrium will move in the direction of the added heat.
w
w

iii. Change in Pressure: The pressure has no effect on the equilibrium if the number of moles of
gaseous reactants and products does not change. The change in pressure in both liquids and
(w

solids can be neglected in heterogeneous chemical equilibrium.

iv. Change in Volume: When the volume of a gaseous mixture at equilibrium is increased, the
equilibrium moves in the direction of a larger number of gaseous molecules.

v. Effect of a Catalyst: The equilibrium is unaffected by the catalyst. This is due to the fact that
the catalyst favours both forward and backward reactions equally.

Homogeneous Equilibria
When in an equilibrium reaction, all the reactants and the products are present in the same phase
(i.e., gaseous or liquid) it is called a homogeneous equilibrium. For example,

N2(g) + 3H2(g) ⇌ 2NH3(g)

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 EQUILIBRIUM
07

Heterogeneous Equilibria
When in an equilibrium reaction, the reactants and the products are present in two or more
than two phases, it is called a heterogeneous equilibrium.

The equilibrium between water vapour and liquid water in a closed container is an example
of heterogeneous equilibrium.

H2O(I) ⇌ H2O(g)

Le Chatelier's Principle
It states that if a stress is applied to a system in equilibrium, the equilibrium for the time
being gets disturbed. As a result system moves in a direction which tends to relieve the

)
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external stress and finally a new equilibrium is attained.

Ionic Equilibrium

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Electrolyte: Electrolytes are the substances which conduct electricity in molten state or in
solution. Example HCl, NaCl, KCl, CH3COOH etc. sa
th
Arrhenius theory of Electrolytic dissociation: When an electrolyte is dissolved in a solvent it
spontaneously dissociates into oppositely charged particles called ions, to a considerable
a

extent. Electrolytic ionization or dissociation gives ions and unionized molecules in solution.
lp

For neutrality, the total charge on cations is equal to the total charge on the anions.
ta

Degree of Dissociation (α): It is the fraction of one mole of the electrolyte that has
gi

dissociated under the given conditions. The value of α depends on temperature, dilution of
i

electrolyte, nature of electrolyte and solvent.

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α = No. of ionized moles/ Total mo. Moles

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Ostwald's Law of Dilution:

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According to this law, "The degree of ionization (or dissociation) of any weak electrolyte is
inversely proportional to the square root of concentration."

K
α= √
C

Where, K = proportionality constant

Concepts of Acids and Bases

1. Arrhenius Concept:
• Acid: Any substance when dissolved in water, increases the concentration of H+. e.g.,
HCl, H2SO4, HNO3 etc.

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 EQUILIBRIUM
07

• Base: Any substance when dissolved in water, increases the concentration of OH-.
e.g., NaOH, KOH etc.

2. Bronsted - Lowry Concept:

• Acid: Species (Molecule or ion) that donates a proton to another species.

• Base: Species (Molecule or ion) that accepts a proton from another species.
HCl(Acid) + NH3(Base) ⟶ NH+4 + Cl-
3. Lewis acids and bases:
According to Lewis concept of acids and bases, a Lewis acid is an electron pair acceptor
and a Lewis base is an electron pair donor.
Lewis acids: H+, Ag+, Fe2+, AlCl3, BF3, BCl3, BeCl2 etc.

)
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Lewis Bases: Cl-, CN-, OH-, X-, NH-2, SH- etc.
An acid base reaction is the sharing of an electron pair with an acid by a base. This

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process is simply defined as coordination or neutralisation.

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a. A strong acid is an acid that ionizes completely in water.
sa
HCl(aq) + H2O (l) ⟶ H3O+ (aq) + Cl-(aq)
th
b. A weak acid is an acid that is only partially ionized in water
a

CH3COOH(aq) + H2O(l) ⇌ CH2COO-(aq) + H3O+(aq)

lp
ta

c. A strong base is a base that ionizes completely in water.

gi

KOH(aq) ⟶ K+(aq) + OH-(aq)

i
.d

d. A weak base is a base which is partially ionized in water

w

NH3(aq) + H2O(l) ⇌ NH+4(aq) + OH–(aq)

w
(w

The pH Scale
pH of solution may be defined as negative logarithm of hydronium ion concentration.
pH = −log [H3 O+ ]
1
pH = log
[H3 O+ ]
The pH range at 25°C is taken as 0 to 14.
pH = 7 Neutral
pH > 7 Basic
pH < 7 Acidic
Common Ion Effect
The suppression in the dissociation of a weak electrolyte by the addition of a strong electrolyte
having a common ion is called common ion effect.

(8)
 EQUILIBRIUM
07

For example: Ionisation of acetic acid (CH3COOH) and effect of addition of a small amount of
acetate ion.

CH3COOH(aq) ⟶ CH3COO-(aq) + H+(aq)

CH3COONa(aq) ⟶ CH3COO-(aq) + Na+(aq)

Buffer Solution
A buffer solution is that solution which resists any change in its pH value on addition of small
amount of acid or base. Although the pH of buffer changes on doing so, but the change in pH
value will be less than the expected change. There are three types of buffer solution.

Acidic Buffer: This consists of solution of a weak acid and its salt with strong base. Example;

)
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CH3COOH and CH3COONa.

Basic Buffer: This consists of solution of weak base and its salt with strong acid. e.g., NH4OH

.c
and NH4Cl

la
Salt Buffer: It is a solution of salt which itself can act as a buffer. Such a salt is the salt of weak
sa
acid and weak base. For example,
th
CH3COONH4 ⇌ NH4+ + CH3COO-
a
lp

When an acid is added, it reacts with CH3COO- to produce CH3COOH and when a base is
added, it react with NH4+ to produce NH4OH.
ta
gi

Buffer Capacity
i
.d

It is the number of moles of acid or base required by one litre of a buffer solution for changing
its pH by one unit.
w
w

Buffer Capacity = No. of moles of acid or base adder per litre / Change in pH
(w

Solubility and Solubility Product

The number of moles of solute in one litre of a saturated solution (mole / L) is defined as
solubility. Let us calculate solubility of salt AgCl.

AgCl ⇌ Ag+ + Cl-

Ksp = [Ag+][Cl-]

Ksp is called solubility product.

In pure water,

Ksp = [Ag+][Cl-]

(9)
 EQUILIBRIUM
07

Ksp = S2 {∵ S = [Ag+] = [Cl-]}

S = √K sp
Salt Hydrolysis

Salt hydrolysis is defined as the process in which a salt reacts with water to give back the acid
and the base.

Salt + water ———-> Acid + Base

BA + H2O ———> HA + BOH

All salts are strong electrolytes and thus ionize completely in the aqueous solution.

)
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(1) If the acid produced is strong and the base produced is weak.

B+ + A‾ + H2O ——-> H+ + A‾ + BOH

.c
la
or

B+ + H2O ——-> H+ + BOH

sa
th
In this case the cation reacts with water to give an acidic solution. This is called cationic
a

hydrolysis.
lp

(2) If the acid produced is weak and the base produced is strong.
ta

B+ + A‾ + H2O ——-> HA + B+ + OH‾

i gi

or
.d
w

A‾ + H2O ——-> HA + OH‾

w

In this case the anion reacts with water to give basic solution. This is called acidic hydrolysis.
(w

Salt hydrolysis may be defined as the reaction of the cation or the anion of the salt with water
to produce acidic or basic solution.

Depending upon the relative strength of the acid and the base produced, the resulting
solution is acidic, basic or neutral.

(1) Salts of strong acid and strong base

NaCl, NaNO3, Na2SO4, KCl, KNO3 , K2SO4

NaCl + H2O ——-> NaOH + HCl

Na+ + Cl‾ + H2O ——-> Na+ + OH‾ + H+ + Cl‾

H2O ——-> OH‾ + H+

(10)
 EQUILIBRIUM
07

It involves only ionization of water and no hydrolysis.So the solution is neutral.

The salts of strong acids and strong bases do not undergo hydrolysis and the resulting solution
is neutral.

(2) Salts of weak acid and strong bases

CH3COONa, Na2CO3, K2CO3, Na3PO4

CH3COONa + H2O ⇌ CH3COOH + NaOH

CH3COO‾ + Na+ + H2O ⇌ CH3COOH + Na+ + OH‾

CH3COO‾ + H2O ——-> CH3COOH + OH‾

)
om
As it produces OH‾ ions, the solution of such a salt is alkaline in nature.

(3) Salts of strong acid and weak base

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la
NH4Cl , CuSO4, NH4NO3 , AlCl3, CaCl2

NH4Cl + H2O ⇌ NH4OH + HCl

sa
th
NH4+ + Cl‾ + H2O ⇌ NH4OH + H+ + Cl‾
a
lp

NH4+ + H2O ——-> NH4OH + H+

ta

As it produces H+ ions, the solution of such a salt is acidic in nature.

gi

(4) Salts of weak acid and weak base

i
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CH3COONH4 , AlPO4 , (NH4) 2CO3

w

CH3COONH4 + H2O ⇌ CH3COOH + NH4OH

w
(w

It involves both anionic and cationic hydrolysis

Hydrolysis constant

Equation for the hydrolysis of a salt (BA) may be written as:

𝐵𝐴 + 𝐻2 𝑂 ⇌ 𝐵𝑂𝐻 + 𝐻𝐴

𝐵+ + 𝐴− + 𝐻2 𝑂 ⇌ 𝐵𝑂𝐻 + 𝐻+ + 𝐴− 𝑜𝑟 𝐵+ + 𝐻2 𝑂 ⇌ 𝐵𝑂𝐻 + 𝐻 +
[𝐵𝑂𝐻][𝐻 + ]
Hydrolysis constant, 𝐾ℎ =
[𝐵 + ]

Degree of Hydrolysis

The degree of hydrolysis of a salt is defined as the function of the total salt which is hydrolyse

(11)
 EQUILIBRIUM
07

i.e.

h = No. of moles of the salt hydrolysed / Total no. of moles the salt taken
Strengths of Acids And Bases

According to Arrhenius concept, an acid is defined as a substance which when dissolved in

water gives H+ and a base is defined as a substance which when dissolved in water give OH‾
ions.

Greater the number of H+ ions produced in the aqueous solution, the stronger is the acid.

Greater the number of OH‾ ions produced in the aqueous solution, the stronger is the base.

)
As greater is the dissociation constant of the weak acid ( Ka ) , greater is the amount of H+ (aq)

om
produced, therefore stronger is the acid.

Ka value gives a measure of the relative strength of the weak acid.

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la
Kb value gives a measure of the relative strength of the weak base.
sa
Suppose the weak acid is represented by HA. Suppose the initial concentration of HA is C
th
mol/L and ∝ is the degree of dissociation.
a

HA + H2O ⇌ H+ (aq) + A‾ (aq)

lp

C 0 0 Initial conc
ta
gi

C (1-∝)C∝ C∝ Conc at equilibrium

i

[𝐻 + ][𝐴−
𝑤𝑒𝑎𝑘 ]
.d

Ka = [𝐻𝐴𝑤𝑒𝑎𝑘 ]
w

where Ka is called dissociation constant of the acid.

w

𝐶𝑎2
(w

𝐾=
1−𝑎
If a is very samall 1- a ≈ 1 ⇒ Ka = Ca2

𝐾𝑎
or a = √
𝐶

If two acids of equimolar concentration are taken

𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑 𝐻𝐴1 𝐾𝑎1

=√
𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑 𝐻𝐴2 𝐾𝑎2

The relative strength of two acids of equimolar concentration can be compared by taking
square root of the ratios of their dissociation constants.

(12)
 EQUILIBRIUM
07

CH3COOH is nearly 192 times stronger than HCN.

The relative strength of two weak bases of equimolar concentration can be compared by
taking square root of the ratios of their dissociation constants.

)
.c om
la
Since the ionization of an acid or a base increases with dilution, the strength of the acid or
sa
base increases with dilution.
th
Ka and Kb are taken as dimensionless quantities because the standard state concentration of
a

all species involved is taken as mol L-1

lp

Polyprotic acid and polyacidic bases

ta
gi

Some acids like H2SO4 , H2CO3, (COOH)2 , H3PO4 , H3AsO4 contain more than one ionizable
proton.Such acids are called polybasic or polyprotic acids.They ionize in steps.
i
.d
w
w
(w

H2A (aq) ⇌ H+ (aq) + HA- (aq)

HA- (aq) ⇌ H+ (aq) + A2- (aq)

(13)
 EQUILIBRIUM
07

[𝐻𝐴1 ][𝐻 + ]
𝐾𝑎1 =
[𝐻2 𝐴]

[𝐴2− ][𝐻+ ]
𝐾𝑎2 =
[𝐻𝐴− ]

Ka = Ka1 × Ka2

For a tribasic acid , the overall ionization constant will be product of the ionization constant of
the three steps i.e.

Ka = Ka1 × Ka2 × Ka3

Ka1 > Ka2 > Ka3

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It is more difficult to remove a positively charged proton from a negative ion due to
electrostatic forces.

.c
Greater the charge on the negative ion, more difficult it becomes to remove a proton.

la
sa
According to Bronsted -Lowry concept , the relative strength of two acids are compared by
comparing their tendencies to donate protons. The relative strength of two bases are
th
compared by comparing their tendencies to accept proton.
a

The relative strength of the two acids or the two bases involved in the two acid-base
lp

conjugate pairs can be found out if we know whether forward reaction is favoured or
ta

backward reaction is favoured.

gi

HCl + H2O ⇌ H3O+ + Cl‾

i
.d

acid1 base2 acid2 base1

w

Acid- Base Titration using Indicator

w

Titration is the measurement of the volume of a solution of one reactant that is required to
(w

react completely with a measured amount of another reactant.

As both the reactants are taken in the form of solution and the titration is the measurement
of volume of one solution that must be added to another solution till the reaction is complete,
this method of quantitative analysis is called volumetric analysis.

The concentration of the solution called as standard solution is known and it is desired to find
the concentration of other by titration.

Apparatus of Titration

(14)
 EQUILIBRIUM
07

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la
sa
a th
lp
ta
i gi
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w
w
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Procedure

1) A known volume of the solution is taken in the titration flask with the help of a pipette.

2) The other solution is taken in the burette which is graduated in cc’s and has a stop cock at
bottom to control the amount of flow into the flask.

3) The solution to be titrated is taken in the flask and is called titrate and the solution with
which the titration is to be done that is taken in the burette is called the titrant.

The point at which the required volume of one solution has been added to the other to
exactly complete the reaction between the two is called end point or equivalence point.

(15)
 EQUILIBRIUM
07

Types of titrations

• Redox titrations involving oxidation and reduction.

• Acid -base titrations involving neutralization

• Precipitation titration

• Complexometric titration involving formation of complexes.

The substance usually added into the solution taken in the titration flask to detect the
equivalence point is called an indicator

Theory of acid base indicators

)
om
Acid base indicators are mostly complex organic molecules which are either weak acid or
weak bases

.c
For ex: Phenolphthalein is a weak organic acid (HPh) and methyl orange is a weak organic

la
base ( MeOH) . sa
Phenolphthalein and methyl orange dissociates in aqueous solution as :
th
HPh ⇌ H+ + Ph‾ ————— (1)
a
lp

colourless pink
ta

MeOH ⇌ Me+ + OH‾ ————– (2)

gi

Yellow red colourless

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The unionized form has one colour and the ions have different colour.
w
w

For Ex: HPh is colourless while Ph ions have pink colour. Similarly , MeOH has yellow colour
while Me+ have red colour.
(w

As the medium changes from acidic to basic or vice versa , the equilibrium shifts either
towards the right or towards the left and so the colour changes.

In acidic medium the equilibrium 1 is towards left and the solution is colourless while in the
basic medium, OH‾ ions will combine with the H+ to form unionized water molecules, the
equilibrium shifts towards the right and the solution has a pink colour.

In methyl orange in basic medium the equilibrium 2 is towards left and the colour is yellow
while in the acidic medium H+ ions combine with the OH‾ ions and the equilibrium 2 shifts
towards the right and the colour is red.

Phenolphthalein cannot be used as an indicator if the base is weak because the OH‾ ions
produced from the weak base are insufficient to shift the equilibrium 1 towards the right.

(16)
 EQUILIBRIUM
07

Methyl orange is not a suitable indicator if the acid is weak because the H+ ions produced are
insufficient to combine with OH‾ ions and shift the equilibrium 2 towards the right.

pH at the end point of acid – base Titration

(1) If strong acid has been titrated with strong base, the pH at the end point is 7.

(2) If a weak acid or a weak base is involved in the titration, pH at the end point depends upon
the hydrolysis of salt formed.In any type of acid-base titration, it is found that there is a
sudden change in the pH value at the end.

As the titration proceeds, if the pH values of the solution are measured or calculated
theoreically and then plotted against the volume of the solution added, the curve obtained is
called titration curve.

)
om
Titration Curve

.c
la
sa
a th
lp
ta
i gi
.d
w
w
(w

The point at which there is sudden change in pH when a very small amount of titrant is added
to the titrate is called point of inflection.

(17)
 EQUILIBRIUM
07

The steepness of the slope around the equivalence point is quite large in case of titration of
strong acid against strong base whereas it is less steep if the acid or base is weak.

Large steepness means large change in pH on adding a very small volume of the solution. It
may be pointed out that if a weak acid is titrated against a weak base, the change in pH at the
end is so small that it is difficult to determine the end.

Selection of a Suitable Indicator

The indicator used should be such that it shows change in colour in the same pH range as
required around the equivalence point.

)
.c om
la
sa
a th
lp
ta
i gi
.d
w
w
(w

(1) For titration of a strong acid against a strong base, any indicator out of methyl orange,
methyl red, phenolphthalein or bromothymol blue can be used to determine the endpoint.

(2) For titration of weak acid like acetic Acid against a strong base, only phenolphthalein is a
suitable indicator.

(3) For titration of weak base against strong acid ,methyl orange or methyl red or
bromothymol blue can be used as an indicator.

(4)For titration of weak acid with weak base ,no indicator is found to function satisfactorily.

Colour change pKindicator =pH at the equivalence point

(18)
 EQUILIBRIUM
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Consider an indicator which is a weak organic acid.Let it be represented by HIn. In aqueous

solution , it dissociates as:

HIn (aq) ⇌ H+ (aq) + In‾ (aq)

HIn and In‾ have different colours.The equilibrium constant for the above reaction is :

Kin = [H+] [In‾ ] / [HIn]

The exact point of colour change will be at the pH when [HIn] = [In‾ ]

Kin = – log kIn = – log [H+]

For a particular titration , the indicator selected should be such for which pKIn = pH

)
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Summary
1. Equilibrium: It represents the state of a process in which the properties like temperature,

.c
pressure, concentration of the system do not show any change with the passage of time.

la
2.
sa
Physical equilibrium: It is a state of equilibrium in which the two opposing processes
involve changes in physical state only.
th
3. Chemical equilibrium: It is a state of equilibrium in which the two opposing processes
a

involve change of chemical species.

lp
ta

4. Reversible reaction: A reversible reaction is one which proceeds in both the forward and
backward directions.
i gi

5. Law of mass action: This law states that at constant temperature, the rate of chemical
.d

reaction is directly proportional to the product of molar concentrations of the reacting

w

substances.
w

6. Equilibrium constant (K): It is the ratio of the product of the molar concentrations of the
(w

substances formed to that of the reacting substances raised to the powers equal to their
stoichiometric coefficients in the chemical equation at a particular temperature.

7. Henry’s law: The mass of a gas dissolved in a given mass of a solvent at any temperature
is directly proportional to the pressure of the gas above the solvent.

8. Le Chatelier’s Principle: When a system in dynamic equilibrium is subjected to a stress

such as a change in concentration, pressure or temperature, the equilibrium shifts in a
direction that opposes or reduces the stress.

9. Strong electrolytes: Electrolytes which are ionized almost completely in aqueous solution
under similar conditions of concentration and temperature are called strong electrolytes.

10. Weak electrolytes: Electrolytes which are poorly ionized in aqueous solution under
similar conditions of concentration and temperature are called weak electrolytes.

(19)
 EQUILIBRIUM
07

11. Solubility product: It is the product of concentration of ions in a saturated solution of a

sparingly soluble salt at a given temperature.

12. Arrhenius acid-base concept: According to Arrhenious, an acid is a substance which gives
hydrogen ions and base is a substance which gives hydroxyl ions in aqueous solutions.

13. Bronsted-Lowry acid-base concept: According to this concept, an acid is a proton donor
and base is a proton acceptor.

14. Lewis acid-bases concept: According to this concept, an acid is an electron pair acceptor
and base is an electron pair donor.

15. pH value: pH value of a solution is the negative logarithm of the hydrogen ion
concentration (in moles per litre) present in it. Thus pH = -log[H+]

)
om
16. Irreversible reaction: If a reaction cannot take place in the reverse direction i.e., the
products formed do not react to give back the reactants under the same conditions is

.c
called an irreversible reaction.

la
17. Homogeneous equilibria: When in an equilibrium reaction, all the reactants and the
sa
products are present in the same phase (i.e., gaseous or liquid), it is called a
th
homogeneous equilibrium.
a

18. Heterogeneous equilibrium: When in an equilibrium reaction, the reactants and the
lp

products are present in two or more than two phases, it is called a heterogeneous
ta

equilibrium.
gi

19. Buffer solution: It is defined as a solution which resists in its pH value even when small
i

amounts of the acid or the base are added to it.

.d
w

20. Conjugate base: A base formed by the loss of proton by an acid is called conjugate base
of the acid.
w
(w

(20)
 07
EQUILIBRIUM

(w
w
w
.d
igi
ta
lp
ath
sa
la
.c om
)

(21)
 07
EQUILIBRIUM

(w
w
w
.d
igi
ta
lp
ath
sa
la
.c om
)

(22)
 EQUILIBRIUM
07

Important Questions

Multiple Choice questions-

Question 1. Which of the following fluoro-compounds is most likely to behave as a Lewis
base?
(a) BF3
(b) PF3
(c) CF4
(d) SiF4

)
Question 2. Calculate the pOH of a solution at 25°C that contains 1 × 10-10 M of hydronium

om
ions, i.e. H3O+.
(a) 4.000

.c
(b) 9.000

la
(c) 1.000 sa
(d) 7.000
th
Question 3. When two reactants, A and B are mixed to give products C and D, the reaction
a

quotient, Q, at the initial stages of the reaction

lp

(a) is zero
ta

(b) Decreases With Time

gi

(c) Is Independent of Time

i
.d

(d) Increases With Time

w

Question 4. 1 M NaCl and 1 M HCl are present in an aqueous solution. The solution is
w

(a) Not a buffer solution with pH < 7

(w

(b) Not a buffer solution with pH > 7

(c) A buffer solution with pH < 7
(d) A buffer solution with pH > 7
Question 5. If, in the reaction N2O4 2NO2, x is that part of N2O4 which dissociates, then the
number of molecules at equilibrium will be
(a) 1
(b) 3
(c) (1 + x)
(d) (1 + xy)²
Question 6. The solubility product of a salt having general formula MX2. In water is: 4 × 10-12.

(23)
 EQUILIBRIUM
07

The concentration of M2+ions in the aqueous solution of the salt is

(a) 4.0 × 10-10 M
(b) 1.6 × 10-4 M
(c) 1.0 × 10-4 M
(d) 2.0 × 10-6 M
Question 7. Equimolar solutions of the following were prepared in water separately. Which
one of the solutions will record the highest pH?
(a) CaCl2
(b) SrCl2
(c) BaCl2

)
om
(d) MgCl2
Question 8. Oxidation number of Iodine varies from

.c
(a) -1 to +1

la
(b) -1 to +7 sa
(c) +3 to +5
th
(d) -1 to +5
a
lp

Question 9. Which of the following molecular species has unpaired electrons?

(a) N2
ta

(b) F2
gi

(c) O–2
i
.d

(d) O2-2
w

Question 10. A certain buffer solution contains equal concentration of X– and HX. The ka for
w

HX is 10-8. The pH of the buffer is

(w

(a) 3
(b) 8
(c) 11
(d) 14
Question 11. Among the following the weakest Bronsted base is
(a) F–
(b) Cl–
(c) Br–
(d) I–
Question 12. Which of the following statements is correct about the equilibrium constant?

(24)
 EQUILIBRIUM
07

(a) Its value increases by increase in temperature

(b) Its value decreases by decrease in temperature
(c) Its value may increase or decrease with increase in temperature
(d) Its value is constant at all temperatures
Question 13. pH value of which one of the following is NOT equal to one.
(a) 0.1 M CH3COOH
(b) 0.1 M HNO3
(c) 0.05 M H2SO4
(d) 50cm³ 0.4 M HCl + 50cm³ 0.2 M NaOH

)
Question 14. [ OH–] in a solution is 1 mol L–. The pH the solution is

om
(a) 1
(b) 0

.c
la
(c) 14
(d) 10-14
sa
th
Question 15. What is the pH of a 0.10 M solution of barium hydroxide, Ba (OH)2?
(a) 11.31
a
lp

(b) 11.7
ta

(c) 13.30
gi

(d) None of these

i
.d

Very Short:
w

1. Write the expression for the equilibrium constant Kp for the reaction 3Fe (s) + 4H2O (g)
w

⇌ Fe3O4 (s) + 4H2 (g)

(w

2. How are Kc and Kp related to each other in the reaction

N2 (g) + O2 (g) ⇌ 2NO (g)
3. What is the equilibrium constant expression for the reaction
3
Al (s) + 3H+ (aq) ⇌ Al3+ (aq) + H2 (g)
2
4. What happens to the equilibrium
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) if nitrogen is added to it
(i) at constant volume
(ii) at constant pressure?
5. What does the equilibrium K < I indicate?
6. For an exothermic reaction, what happens to the equilibrium constant if the

(25)
 EQUILIBRIUM
07

temperature is increased?
7. Under what conditions, a reversible process becomes irreversible?
8. What is the effect of increasing pressure on the equilibrium?
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)?
9. For which of the following cases does the reaction go farthest to completion: K = 1, K =
1010, K = 10-10.
10. Under what conditions ice water system is in equilibrium?
(a) at 273 K
(b) below 273 K
(c) above 273 K.

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Short Questions:

.c
1. Justify the statement that water behaves like acid as well as a base on the basis of the

la
protonic concept.
2.
sa
What is pOH? What is its value for pure water at 298 K?
th
3. Calculate the pH of a buffer solution containing 0.1 moles of acetic acid and 0.15 mole
of sodium acetate. The ionization constant for acetic acid is 1.75 × 10-5.
a
lp

4. An aqueous solution of CuSO4 is acidic while that of Na2SO4 is neutral. Explain.

ta

5. The dissociation constants of HCN, CH3COOH, and HF are 7.2 × 10-10, 1.8 × 10-5, and 6.7
× 10-4 respectively. Arrange them in increasing order of acid strength.
gi

6. The dissociation of PCl5 decreases in presence of Cl2. Why?

i
.d

Long Questions:
w
w

1. Explain chemical equilibrium with th^ help of an example of formation and

(w

decomposition of hydrogen iodide.

2. Name and explain the factors which influence the equilibrium state.
3. What is salt hydrolysis? Explain hydrolysis of salts of
(i) strong acids and strong bases
(ii) strong acids and weak bases
(iii) strong bases and weak acids
(iv) strong acids and weak bases.
N
4. Calculate the pH of Sodium hydroxide solution assuming complete ionisation (Kw =
1000
1.0 × 10-14).
5. Calculate the pH of a 0.01 N solution of acetic acid. Ka for acetic acid is 1.8 × 10-5 at 25°C

(26)
 EQUILIBRIUM
07

Assertion Reason Questions:

1. In the following questions, a statement of Assertion (A) followed by a statement of
Reason (R) is given. Choose the correct option out of the choices given below each
question.

Assertion (A) : Increasing order of acidity of hydrogen halides is HF < HCl < HBr < HI
Reason (R) : While comparing acids formed by the elements belonging to the same group
of periodic table, H–A bond strength is a more important factor in determining acidity of
an acid than the polar nature of the bond.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.

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(iii) A is true but R is false.
(iv) Both A and R are false.

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2. In the following questions, a statement of Assertion (A) followed by a statement of
Reason (R) is given. Choose the correct option out of the choices given below each
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question.
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Assertion (A) : A solution containing a mixture of acetic acid and sodium
a

acetate maintains a constant value of pH on addition of small

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amounts of acid or alkali.

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Reason (R) : A solution containing a mixture of acetic acid and sodium

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acetate acts as a buffer solution around pH 4.75.

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(i) Both A and R are true and R is correct explanation of A.

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(ii) Both A and R are true but R is not the correct explanation of A.
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(iii) A is true but R is false.

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(iv) Both A and R are false.

Case Study Based Question:
1. Le Chatelier’s principle is also known as the equilibrium law, used to predict the effect of
change on a system at chemical equilibrium. This principle states that equilibrium adjusts
the forward and backward reactions in such a way as to accept the change affecting the
equilibrium condition. When factor-like concentration, pressure, temperature, inert gas
that affect equilibrium are changed, the equilibrium will shift in that direction where the
effects caused by these changes are nullified. This principle is also used to manipulate
reversible reactions in order to obtain suitable outcomes.
(1) Which one of the following conditions will favour the maximum formation of the
product in the reaction?

(27)
 EQUILIBRIUM
07

(a) Low temperature and high pressure

(b) Low temperature and low pressure
(c) High temperature and high pressure
(d) High temperature and low pressure

(2) For the reversible reaction,

)
The equilibrium shifts in forwarding direction

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(a) By increasing the concentration of NH3(g)
(b) By decreasing the pressure

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(c) By decreasing the concentrations of N2(g) and H2(g)
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(d) By increasing pressure and decreasing temperature
th
(3) Favourable conditions for manufacture of ammonia by the reaction,
a
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(a) Low temperature, low pressure and catalyst

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(b) Low temperature, high pressure and catalyst

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(c) High temperature, low pressure and catalyst

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(d) High temperature, high pressure and catalyst

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(4) For the above equilibrium, the reactant concentration is doubled, what would happen
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then to equilibrium constant?

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(a) Remains constant

(b) Be doubled
(c) Be halved
(d) Cannot be predicted

(5) In which one of the following equilibria will the point of equilibrium shift to left when
the pressure of the system is increased?

(28)
 EQUILIBRIUM
07

Answer Key:
MCQ
1. (b) PF3

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2. (a) 4000

3. (d) Increases With Time

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4. (a) Not a buffer solution with pH < 7

5. (a) 1
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6. (c) 1.0 × 10-4 M
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7. (c) BaCl2
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8. (b) -1 to +7
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9. (c) O–2
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10.(b) 8
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11.(d) l-
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12.(c) Its value may increase or decrease with increase in temperature

13.(a) 0.1 M CH3COOH

14.(c) 14

15.(c) 13.30

Very Short Answer:

1.

(29)
 EQUILIBRIUM
07

2. Kp = Kc.

3. Kc = [Al3+ (aq)][H2 (g)3/2/[H+ (aq)]3.

4. The state of equilibrium remains unaffected.

(ii)Dissociation increases, i.e., the equilibrium shifts forward.

5. The reaction does not proceed much in the forward direction.

6. K = K/Kb.

Kb increases much more than when the temperature is increased in an exothermic reaction.

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Hence K decreases.

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7. If one of the products (gaseous) is allowed to escape out (i.e., in the open vessel).

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8. Equilibrium will shift in the forward direction forming more ammonia

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9. The reaction having K = 1010 will go farthest to completion because the ratio
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(product)/(reactants) is maximum in this case.
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10. (a) At 273 K.
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Short Answer:
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Ans: 1. Water ionizes as H2O + H2O ⇌ H3O+ + OH–

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With strong acids, water behaves as a base by accepting a proton from an acid.
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HCl + H2O ⇌ H3O+ (aq) + Cl– (aq)

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While with bases, water behaves as an acid by liberating a proton

NH3 + H2O ⇌ NH4+ (aq) + OH (aq).

Ans: 2. pOH = – log [OH–]

pH + pOH = 14 for pure water at 298 K
pH = 7
or
pOH of water at 298 = 7.

Ans: 3.

(30)
 EQUILIBRIUM
07

Ans: 4. CuSO4 + 2H2O ⇌ Cu (OH)2 + H2SO4 (weak base strong acid)

CuS04 is the salt of weak base Cu (OH)2 and a strong acid H2SO4.

Thus, the solution will have free H+ ions and will, therefore, be acidic.

Na2SO4, being the salt of a strong acid H2SO4 and a strong base.

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NaOH does not undergo hydrolysis. The solution is, therefore, neutral.

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Ans: 5. More the value of Ka, the stronger the acid

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Their Ka1S are 6.7 × 10-4 > 1.8 × 10-5 > 7.2 × 10-10 sa
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∴ HCN < CH3COOH < HF.
a

Ans: 6. For PCl5 ⇌ PCl3 + Cl2.

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According to Le Chatelier’s principle, an increase in the concentration of Cl2 (one of the

products) at equilibrium will favor the backward reaction, and thus the dissociation of PCl5
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into PCl3 and Cl2 decreases

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Long Answer:
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Ans: 1. Consider the reaction between hydrogen and iodide at a constant temperature of
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720 K in a closed vessel. The reaction involved is:

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H2(g) + I2(g) → 2HI(g)

Accordingly, the effective collision amongst the reactant molecules will result in the
production of HI. Since the product molecules are not permitted to leave the vessel (i.e., the
reaction is carried out in a closed vessel), they will also collide amongst themselves leading
to the formation of reactant molecules. Under these conditions, the reaction takes place in
both directions. Hence, it is called a reversible reaction.

(31)
 EQUILIBRIUM
07

Graphical representation of the change of reaction rates with time for the formation and
decomposition of hydrogen iodide

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Forward reaction: H2 (g) + I2 (g) → 2HI (g)

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Backward reaction: 2HI (g) → H2 (g) + I2 (g)

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Reversible reaction: H2 (g) + I2 (g) ⇌ 2HI (g). sa
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To begin with, with the concentration of the reactants being higher in comparison to the
product molecules, the rate of the forward reaction will be high as compared to the
a

backward reaction. As the reaction proceeds further, the molar concentration of the
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reactants will gradually decrease while that of the product will gradually increase.
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Apparently, the rate of forwarding reaction goes on decreasing while that of the backward
reaction. This state is the reversible chemical reaction is called a chemical equilibrium state.
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Ans: 2. The various factors which influence the equilibrium state are:
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1. Concentration: Concentration change influences the equilibrium state. If the

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concentration of the reactants is increased, the equilibrium will shift in such a direction
in which more to the products are formed and vice-versa.
On the other hand, if the concentration of the products is increased, the equilibrium will
shift in such a direction in which more of the reactants are formed.

2. Temperature: Like concentration, the temperature change also affects the equilibrium
state. An increase in temperature of the system will shift the equilibrium in such a
direction in which heat is absorbed (i.e. rate of endothermic reaction will increase).

On the other hand, a decrease in temperature of the system will shift the equilibrium in
such a direction in which heat is evolved (i.e., rate of exothermic reaction will increase).

3. Pressure: Like concentration and temperature, the pressure also influences the

(32)
 EQUILIBRIUM
07

equilibrium state only when the reaction proceeds with a change in volume. An increase
in pressure of the system will shift the equilibrium in such a direction in which the
volume of the system decreases.

On the other hand, a decrease in pressure of the system will shift the equilibrium in such a
direction in which the volume of the system increases.

To explain the effect of temperature, pressure, and concentration on the equilibrium state,
consider the combination of N2 and H2 to form NH3
N2 (g) + 3H2 (g) ⇌ 2NH3 (g); ΔH = – 93.6 kJ

The reaction is reversible, exothermic, and accompanied by a decrease in volume.

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Effect of temperature: According to Le-Chatelier’s principle, an increase in temperature

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shifts the equilibrium in the direction in which heat is absorbed, and a decrease in
temperature shifts the equilibrium in the direction in which heat is evolved. Since the

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formation of ammonia is accompanied by the evolution of heat, it is favored by a decrease in
temperature.

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sa
Effect of pressure: According to Le-Chatelier’s principle, an increase of pressure on a system
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in equilibrium, favors the direction which is accompanied by a decrease in volume and vice-
versa. While going from, left to right in the above reaction, there is a decrease in the number
a

of moles or say volume, the formation of ammonia is favored by an increase in pressure.

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Effect of concentration: According to Le-Chatelier’s principle, an increase of concentration of

any of the substances in the system shifts the equilibrium in the direction in which the
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concentration of that substance is reduced. Thus, the addition of N2 or H2 favors the

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formation of ammonia.
Ans: 3. Salt hydrolysis: Hydrolysis is a process in which a salt reacts with water to form acid
w

and base.
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Salt + Water ⇌ Acid + Base

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B A + H2O ⇌ HA + BOH

That is the interaction of the cations of the salt with OH ions furnished by water and anions
of the salt with H+ ions furnished by water to form an acidic or basic solution is called salt
hydrolysis.
(i) Salts of strong acids and strong bases like NaCl, KCl, KNO3 NaNO3, Na2SO4, K2SO4 do not
undergo hydrolysis because the acids and bases furnished by them in aqueous solutions are
strong acids and strong bases which are completely dissociated.
NaCl + H2O ⇌ NaOH + HCl
NaOH (aq) ⇌ Na+ + OH–
HCl (Aq) ⇌ H+ + Cl–

Since [H+] = [OH–] the resulting solution is neutral and its pH = 7.

(33)
 EQUILIBRIUM
07

(iii) Hydrolysis of salts of strong acids and weak bases:

The salts belonging to this type are NH4NO3, NH4Cl, (NH4)2SO4, CuSO4, AlCl3, Ca(NO3)2, etc.

Let us take the case of NH4NO3

NH4NO3 + H2O ⇌ NH4OH + HNO3
NH4+ + NO3– + H2O ⇌ NH4OH + HNO3
or
NH4+ + H2O ⇌ NH4OH + H+

The resulting solution after hydrolysis is basic (pH > 7). Since only the anions of the salt have
taken place in the hydrolysis, it is called anionic hydrolysis.

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(iv) Hydrolysis of salts of weak acids and weak bases:

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The salts belonging to this type are:
CH3COONH4, (NH4)2CO3, Ca3(PO4)2 etc.

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Let us take the case of hydrolysis of CH3COONH4

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CH3COONH4 + H3O ⇌ CH3COOH + NH4OH sa
or
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CH3COO̅ + NH4 + H2O ⇌ CH3COOH + NH4OH
a

Since both the cations and anions of the salt have participated in the hydrolysis, it is known
lp

as cationic as well as anionic hydrolysis. The nature of the solution or pH depends upon the
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relative strengths of the acid and base that are formed on hydrolysis.
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Ans: 4. Since NaOH is completely ionized

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∴ [NaOH] = [OH–] = 10-3 N = 10-3 M

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Ans: 5.
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Applying the law of chemical equilibrium

Ka = [CH3COO̅ ][H3O+]/[CH3COOH]

(34)
 EQUILIBRIUM
07

Assertion Reason Answer:

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1. (i) Both A and R are true and R is the correct explanation of A.

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2. (i) Both A and R are true and R is the correct explanation of A.

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Case Study Answer:

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1. Answer:
sa
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(1) (a) Low temperature and high pressure
a

(2) (d) By increasing pressure and decreasing temperature

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(3) (b) Low temperature, high pressure and catalyst

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(4) (a) Remains constant

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(35)
CHEMISTRY

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CHAPTER 8: REDOX REACTIONS

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 REDOX REACTIONS
08

REDOX REACTIONS

Introduction

Redox reaction is related to gain or loss of electrons. Reaction in which oxidation and reduction
takes place simultaneously is called redox reaction. This chapter deals with problems based on
redox reactions, oxidation number and balancing of redox reactions by ion, electron method
and oxidation number method.

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Oxidation Reactions

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Oxidation is defined as the addition of oxygen/electronegative element to a substance or
rememoval of hydrogen/ electropositive element from a susbtance.

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2Mg(s) + O2(g) ⟶ 2MgO(s)

Mg(s) + Cl2(g) ⟶ MgCl2(s)

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Reduction Reactions
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Reduction is defined as the memoval of oxygen/electronegative element from a substance or

addition of hydrogen or electropositive element to a substance.
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2FeCl3(aq) + H2(g) ⟶ 2FeCl2(aq) + 2HCl(aq)

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2HgO(s) ⟶ 2Hg(l) + O2(g)

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Oxidation Number or Oxidation State

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Oxidation number for an element is the arbitrary charge present on one atom when all other
atoms bonded to it are removed. For example, if we consider a molecule of HCl, the Cl atom is
more electronegative than H-atom, therefore, the bonded electrons will go with more
electronegative chlorine atom resulting in formation of H+ and Cl- ions. So oxidation number of
H and Cl in HCl are +1 and –1 respectively.

The following points are important to determine the oxidation number of an element.

1. The oxidation number of an atom in pure elemental form is considered to be zero. e.g., H2,
O2, Na, Mg.

(1)
 REDOX REACTIONS
08

2. Oxidation number of any element in simple monoatomic ion will be equal to the charge on
that ion, for example, oxidation number of Na in Na+ is +1.
3. Oxidation number of fluorine in its compound with other elements is always -1.
4. Oxidation number of oxygen is generally -2 but in case of peroxide (H2O2) oxygen has
oxidation number -1. In a compound OF2 the oxidation number of oxygen is +2.
5. The oxidation number of alkali metals (Na, K) and alkaline earth metals (Ca, Mg) are +1 and
+2 respectively.

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6. The oxidation number of halogens is generally -1 when they are bonded to less

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electronegative elements.
7. Oxidation number of hydrogen is generally +1 in most of its compounds but in case of metal

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hydride (NaH, CaH2) the oxidation number is hydrogen is -1.

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8. The algebraic sum of the oxidation numbers of all the atoms in a neutral compound is zero.
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In an ion, the algebraic sum of oxidation number is equal to the charge on that ion.
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Oxidising and Reducing Agent

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A substance which undergoes oxidation acts as a reducing agent while a substance which
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undergoes reduction acts as an oxidising agent. For example, we take a redox reaction,
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Zn + Cu2+ ⟶ Zn2+ + Cu
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In this reaction, Zn is oxidised to Zn2+ so Zn is reducing agent and Cu2+ is reduced to Cu so Cu2+ is
w

an oxidising agent.
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Types of Redox Reactions

1. Combination reactions

A combination reaction is a reaction in which two or more substances combine to form a single
new substance. Combination reactions can also be called synthesis reactions. The general form
of a combination reaction is:

A + B ⟶ AB

Na(s) + Cl2(g) ⟶ 2NaCl(s)

(2)
 REDOX REACTIONS
08

2. Decomposition reactions

A decomposition reaction is a reaction in which a compound breaks down into two or more
simpler substances. The general form of a decomposition reaction is:

AB ⟶ A + B

2HgO(s) ⟶ 2Hg(l) + O2(g)

3. Displacement reactions

Displacement reaction is a chemical reaction in which a more reactive element displaces a less

)
reactive element from its compound.

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CuSO4(aq) + Zn(s) ⟶ ZnSO4(aq) + Cu

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4. Disproportionation reactions

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The reactions in which a single reactant is oxidized and reduced is known as Disproportionation

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reactions. The disproportionation reaction is given below.

2H2O2 ⟶ 2H2O + O2
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Balancing of Redox Reactions

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a. Oxidation Number Method

In this method number of electrons lost in oxidation must be equal to number of electrons
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gained in reduction. Following rules are followed for balancing of reactions:

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1. Write the skeletal equation of all the reactants and products of the reaction.
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2. Indicate the oxidation number of each element and identify the elements undergoing
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change in oxidation number.

3. Equalize the increase or decrease in oxidation number by multiplying both reactants and
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products undergoing change in oxidation number by a suitable integer.

4. Balance all atoms other than H and O, then balance O atom by adding water molecules to
the side short of O-atoms.
5. In case of ionic reactions:

i. For acidic medium: First balance O atoms by adding H2O molecules to the side deficient
in O atoms and then balance H-atoms by adding H+ ions to the side deficient in H atoms.

ii. For basic medium: First balance O atoms by adding H2O molecules to whatever side
deficient in O atoms. The H atoms are then balanced by adding H2O molecules equal in
number to the deficiency of H atoms and an equal number of OH– ions are added to the
opposite side of the equations.

(3)
 REDOX REACTIONS
08

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b. Ion-Electron Method
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1. Write the skeleton equation and indicate the oxidation number of all the elements which
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appear in the skeletal equation above their respective symbols.
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2. Find out the species which are oxidised and which are reduced.
ita

3. Split the skeleton equation into two half reactions, i.e., oxidation half reaction and reduction
half reaction.
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4. Balance the two half reaction equations separately by the rules described below:
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i. In each half reaction, 1st balance the atoms of the elements which have undergone a
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change in oxidation number.

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ii. Add electrons to whatever side is necessary to make up the difference in oxidation
number in each half reaction.

iii. Balance oxygen atoms by adding required number of H2O molecules to the side deficient
in O atoms.

In the acidic medium, H atoms are balanced by adding H+ ions to the side deficient in H-
iv.
atoms. However, in the basic medium, H atoms are balanced by adding H 2O molecules
equal in number to the deficiency of H atoms and an equal number OH – ions are included
in the opposite side of the equation.
5. The two half reactions are then multiplied by suitable integers so that the total number of
electrons gained in one half of the reaction is equal to the number of electrons lost in the other

(4)
 REDOX REACTIONS
08

half reaction. The two half reactions are then added up.

6. To verify whether the equation thus obtained is balanced or not, the total charge on either
side of the equation must be equal.

Galvanic Cell and Electrode Potential

A galvanic cell or voltaic cell is simple electrochemical cell in which a redox reaction is used to
convert chemical energy into electrical energy. It means electricity can be generated with the
help of redox reaction in which oxidation and reduction takes place in two separate
compartments. Each compartment consists of a metallic conductor and dipped in suitable

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electrolytic solution of same metal. Metallic rod acts as electrode.

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The compartment having electrode dipped in solution of electrolyte is known as half-cell and a
half cell has a redox couple. A redox couple means a solution having reduced and oxidised form
of a substance together, taking part in oxidation or reduction half reaction. It is depicted as M +n

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/ M i.e., oxidised form / reduced form. To prepare a galvanic cell two half cells are externally

a
connected through a conducting wire and internally through salt bridge.
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Anodic oxidation: Zn2 ⟶ Zn+2(aq) + 2e(s)

Cathodic reduction: Cu+2(aq) + 2e ⟶ Cu(s)

Net reaction: Zn(s) + Cu+2(aq) ⟶ Zn+2(aq) + Cu(s)

This cell can be briefly presented in one line, known as cell notation i.e.,

Zn | Zn+2 || Cu+2 | Cu

Summary-
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 REDOX REACTIONS
08

1. Oxidation number: Charge on atom which appears on it when it is present in the

combined state.
2. Sum of the oxidation states in a compound/ion should be equal to the zero or to the net
charge on the ion.
3. Some elements show variable oxidation states.
4. Oxidation: The process in which electrons are lost.
5. Reduction: The process in which electrons are gained.
6. Oxidising agent: A substance which oxidises the other.
7. Reducing agent: A substance which reduces the other.
8. Redox reaction: When oxidation and reduction take place together is known as redox
reaction.

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9. Disproportionation reaction: The reaction in which same species is simultaneously
oxidised as well as reduced.

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10. The change in oxidation state of any element in a compound is useful in calculating the
equivalent weight.

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11. Electrochemical series: Arrangement of E°red of different electrodes in increasing order of

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electrode potential.
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12. Electrode Potential: The tendency of an electrode to lose or gain electrons is called
electrode potential.
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13. The standard electrode potentials of a large number of electrodes have been determined
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using standard hydrogen electrode as the reference electrode. By convention, the

standard electrode potential (E°) of hydrogen electrode is 0.00 volts.
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(6)
 08

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REDOX REACTIONS

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(7)
 REDOX REACTIONS
08

Important Questions
Multiple Choice questions-
Question 1. KMnO4 reacts with oxalic acid according to the equation 2MnO 4– + 5C2O42- + 16H+
→ 2Mn2+ + 10CO2 + 8H2O Here 20 mL of 0.1 M KMnO4 is equivalent to
(a) 50 mL of 0.5 M C2H2O4
(b) 20 mL of 0.1 M C2H2O4
(c) 20 mL of 0.5 M C2H2O4
(d) 50 mL of 0.1 M C2H2O4

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Question 2. Which of the following is a redox reaction?
(a) NaCl + KNO3 → NaNO3 + KCl

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(b) Mg(OH)2 + 2NH4Cl → MgCl2 + 2NH4OH

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(c) CaC2O4 + 2HCl → CaCl2 + H2C2O4

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(d) 2Zn + 2AgCN → 2Ag + Zn(CN)2 hs
Question 3. The reduction potential values of M, N and O are +2.46 V, -1.13 V, -3.13 V
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respectively. Which of the following orders is correct regarding their reducing property?
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(a) O > N > M

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(b) M > O > N

(c) M > N > O
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(d) O > M > N

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Question 4. Which of the following processes does not involve either oxidation or reduction?
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(a) Formation of slaked lime from quick lime

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(b) Heating Mercuric Oxide

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(c) Formation of Manganese Chloride from Manganese oxide

(d) Formation of Zinc from Zinc blende
Question 5. The number of moles of KMnO4 reduced by one mole of KI in alkaline medium is
(a) One
(b) Two
(c) Five
(d) One fifth.
Question 6. What is known as Autooxidation?

(8)
 REDOX REACTIONS
08

(a) Formation of H2O by the oxidation of H2O2.

(b) Formation of H2O2 by the oxidation of H2O.
(c) Both (1) and (2) are true
(d) None of the above
Question 7. Which of the following statements regarding sulphur is incorrect?
(a) S2 molecule is paramagnetic.
(b) The vapour at 200° C consists mostly of S8 rings.
(c) At 600°C the gas mainly consists of S2 molecules.

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(d) The oxidation state of Sulphur is never less than +4 in its compounds.

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Question 8. The oxidation number of Xe in BaXeO6 is

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(a) 8

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(b) 6

a
(c) 4
(d) 10
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Question 9. CrO5 has structure as shown, the oxidation number of chromium in the compound
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is?
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(a) +10
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(b) +6
(c) +4
(d) +5
Question 10. Pure water is bad conductor of electricity because
(a) It has high boiling point
(b) It is almost unionised
(c) Its molecules are associated with H- bonds
(d) Its pH is 7 at 25°C
Question 11. The oxidation process involves

(9)
 REDOX REACTIONS
08

(a) Increase in oxidation number

(b) Decrease in oxidation number
(c) No change in oxidation number
(d) None of the above
Question 12. The ionic mobility of alkali metal ions in aqueous solution is maximum for
(a) Li+
(b) Na+
(c) K+

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(d) Rb+

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Question 13. Pure water is bad conductor of electricity because

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(a) It has high boiling point

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(b) It is almost unionised

a
(c) Its molecules are associated with H- bonds
(d) Its pH is 7 at 25°C
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Question 14. The oxidation number of Fe in K4 [Fe (CN)6] is
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(a) 3
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(b) 4
(c) 2
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(d) Zero
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Question 15. A standard hydrogen electrode has zero electrode potential because
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(a) Hydrogen is easiest to oxidise

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(b) This electrode potential is assumed to be zero

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(c) Hydrogen atom has only one electron

(d) Hydrogen is the lightest element

Very Short:
1. What are redox reactions? Give an example.
2. Define oxidation and reduction in terms of electrons.
3. Define an oxidizing agent. Name the best oxidizing agent.
4. What is meant by reducing agent? Name the best reducing agent.
5. In the reaction MnO2 + 4HCl → MnCl2 + H2O which species is oxidized?

(10)
 REDOX REACTIONS
08

6. What is the oxidation state of Ni in Ni (CO)4?

7. What is a redox couple?
8. Define oxidation and reduction in the term of oxidation numbers.
9. What is the sum of oxidation numbers of all atoms in HIO44?
10. What is the oxidation number of N in (NH4)2 SO2?

Short Questions:
1. HNO3 acts only as an oxidant whereas HNOz acts both as an oxidant and reductant.
Why?

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2. Balance the following equation by the ion-electron method.

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Zn(s) + NO3– → Zn2+(aq) + NH+ (aq) + H2O(l) (In acid solution)
3. Balance the following equation in acidic medium by oxidation number method.

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4. Indicate the oxidising and reducing agent in the following reactions:

a
5. hs
Which of the following redox reaction is oxidation & which is reduction?
6. What are the minimum and maximum oxidation numbers shown by sulfur?
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Long Questions:
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1. What are the minimum and maximum oxidation numbers shown by sulfur?
ig

2. Starting with the correctly balanced half-reaction, write the overall net ionic equation for
the following change:
.d

3. Write the method used for balancing redox reaction by oxidation number method.
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4. Determine the oxidation number of O in the following: OF2, Na2O2 & CH3COOH
w

(i) OF2
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(ii) Na2O2
(ii) CH3COOH
5. Determine the volume 6f M/8 KMnO4 solution required to react completely with 25.0
cm3 of M/4 FeSO4 solution in an acidic medium.

Assertion Reason Questions:

1. In the following questions, a statement of Assertion (A) followed by a statement of Reason
(R) is given. Choose the correct option out of the choices given below each question.

Assertion (A) : Among halogens fluorine is the best oxidant.

(11)
 REDOX REACTIONS
08

Reason (R) : Fluorine is the most electronegative atom.

(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

2. In the following questions, a statement of Assertion (A) followed by a statement of Reason

(R) is given. Choose the correct option out of the choices given below each question.

Assertion (A): In the reaction between potassium permanganate and

)
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potassium iodide, permanganate ions act as oxidising agent.

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Reason (R) : Oxidation state of manganese changes from +2 to +7 during
the reaction.

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(i) Both A and R are true and R is the correct explanation of A.

a
(ii) Both A and R are true but R is not the correct explanation of A.
hs
(iii) A is true but R is false.
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(iv) Both A and R are false.
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Case Study Based Question:

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1. Read the passage given below and answer the following questions:
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The oxidation state of an individual atom is 0. The total oxidation state of all atoms in a
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neutral species is 0 and in an ion is equal to the ion charge. Group 1 metals have an
oxidation state of + 1 and group 2 an oxidation state of + 2.
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The oxidation state of fluorine is – 1 in compounds. Hydrogen generally has an oxidation

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state of + 1in compounds. Oxygen generally has an oxidation state of − 2 in compounds.

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In binary metal compounds, group 17 elements have an oxidation state of − 1, group 16

elements of − 2, and group 15 elements of − 3. The sum of the oxidation states is equal to
zero for neutral compounds and equal to the charge for polyatomic ion species. An atom is
oxidised if its oxidation number increases and an atom is reduced if its oxidation number
decreases.
The atom that is oxidised is the reducing agent and the atom that is reduced is the
oxidising agent.

(1) One mole of acidified K2 Cr2 O7 on reaction with excess KI will liberate n mole of I2 then
the value of n is:
(a) 6

(12)
 REDOX REACTIONS
08

(b) 1
(c) 3
(d) 7
(2) When electrons are transferred from Zn to Cu2+ in copper sulphate solution, the energy
(heat) is:
(a) Absorbed
(b) Evolved
(c) Consumed

)
(d) Both (a) and (b)

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(3) Negative Eө indicates that redox couple is

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(a) Weaker reducing agent than H+/ H2 couple

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(b) Stronger reducing agent than H+/ H2 couple

a
(c) Stronger oxidising agent than H+/ H2 couple
hs
(d) Weaker oxidising agent than H+/ H2 couple
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(4) Which of the following statements is/are incorrect?
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(a) The reactants, which undergo oxidation and reduction are called reductant and
oxidant respectively
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(b) In redox reaction, the oxidation number of oxidant increases, while that of reductant
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decreases
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(c) HNO2 acts as an oxidising as well as reducing agent

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(d) Oxidation is the process, in which electrons are lost

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2. Read the passage given below and answer the following questions:
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The concept of electron transfer is found unable to explain the redox changes or electron
shift in case of covalent compounds.
To explain these changes a new concept, called oxidation number is introduced. Oxidation
number is defined as the charge that an atom of the element has in its ion or appear to
have when present in the combined state with other atoms. In other words, it is also
defined as the charge that an atom appear to have in a compound when all other atoms
are removed as ions from the compound.
The following steps are involved while calculating the oxidation number of an atom in a
given compound/ ion.
Step I Write down the formula of given compound/ion leaving some space between the
atoms.

(13)
 REDOX REACTIONS
08

Step II Write the oxidation state of each element above its atoms. Write down x above
the atom, oxidation state of which we have to find out.
Step III Multiply the oxidation numbers of each element with the number of atoms of
that element present in the compound. Enclose the product in a bracket.
Step IV Equate the algebraic sum of the oxidation numbers of all the atoms present in
compound to zero or to the charge in case of ionic species charge on the ion.
Step V Solve the equation obtained for the value of x.

(1) Highest oxidation state of Mn is present in:

(a)KMnO4

)
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(b)K2MnO4

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(c)M2nO3
(d)MnO2

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(2) Identify the element which never has positive oxidation number in any of its

a
compound? hs
(a) Oxygen
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(b) Chlorine
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(c) Fluorine
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(d) Bromine
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(3) When a manganous salt is fused with a mixture of KNO 3 and solid NaOH, the oxidation
number of Mn changes, from + 2 to:
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(a) + 4
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(b) + 3
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(c) + 6
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(d) + 7
(4) The brown ring complex compound is formulated as [Fe(H2O)5 NO]SO4. What will be the
oxidation state of iron in the given complex?
(a) + 2
(b) + 3
(c) + 4
(d) + 1

Answer Key:

(14)
 REDOX REACTIONS
08

MCQ
1. (d) 50 mL of 0.1 MC2H2O4

2. (d) 2Zn + 2AgCN → 2Ag + Zn(CN)2

3. (d) O > M > N

4. (a) Formation of slaked lime from quick lime

5. (b) Two

)
6. (b) Formation of H2O2 by the oxidation of H2O.

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7. (d) The oxidation state of sulphur is never less than +4 in its compounds.

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8. (d) 10

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9. (b) +6

a
10.(b) It is almost unionised
hs
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11.(a) Increase in oxidation number
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12.(d) Rb+
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13.(b) It is almost unionised

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14.(c) 2
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15.(b) This electrode potential is assumed to be zero

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Very Short Answer:

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1. Redox reaction is a reaction in which oxidation and reduction take place simultaneously,
e.g.
Zn (s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

2. Oxidation involves loss and reduction involves the gain of electrons.

3. The oxidizing agent is a substance that can gain electrons easily. F2 is the best oxidizing
agent.

4. The reducing agent is a substance that can lose electrons easily. Li is the best reducing agent

(ii)Dissociation increases, i.e., the equilibrium shifts forward.

(15)
 REDOX REACTIONS
08

5. HCl is oxidized to Cl2

6. Zero

7. The redox couple consists of the oxidized and reduced form of the same substance taking
part in an oxidation or reduction half-reaction, for example.
Zn2+(aq) / Zn, Cl2 / Cl–(aq) etc.
8. Oxidation involves an increase in oxidation number while reduction involves a decrease in
oxidation number.

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Sn2+ + 2Hg2+ → Sn4+ + Hg2+

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Here Sn2+ gets oxidised while Hg2+ gets reduced.
9. Zero

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10.

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The oxidation number of N is (NH4)2 SO4 is – 3.

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Short Answer:
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Ans: 1. Ox. No. of N in HNO3 = +5

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Ox No. of N in HNO2 = +3

Maximum oxidation numbers which N can show is = + 5

(∴ It has only 5 valance electrons 2S22P3)

The Ox. No. of N in HNO3 is maximum and it can only decrease. Therefore, HNO3 can act only
as an oxidant. Minimum Ox. No. of N is -3.

Thus, HNO2 in which Ox. No. of N is +3 Can decrease as well as increase. Thus, HNO2 can act as
an oxidant as well as a reductant.

(16)
 REDOX REACTIONS
08

Ans: 2. Oxidation half reaction

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Multiply (1) equation by 4 to equalize the no. of electron in both. Add both half reaction
4 Zn(s) → Zn2+(aq) + 8e–

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Zn(s) + NO3– (aq) + 10H+ (aq) → 4Zn2+ (aq) +NH+(aq)+ 3H22O(1)

a
– 1 + 10 = + 8 + 1
+9=+9
Ans: 3.
hs
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ig
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Ans: 4. (i) 2Mg + SO2 → 2MgO + S

Mg = Reducing agent

SO2 = Oxidising agent

(17)
 REDOX REACTIONS
08

(ii)2Cu2+ + 41 → 2CuI + I2

Cu2+ = Oxidising agent

I- = Reducing agent

(iii)SO2 + 2H2S → 2H2O + 3S

SO2 = Oxidising ageiit

H2S = Reducing agent

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(iv)Sn2+ + 2Hg2+ → Hg22+ + Sn4+

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Sn2+ = Reducing agent

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Hg2+ = Oxidising agent

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Ans: 5. (i) Zn → Zn2+ + 2e–
hs
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Oxidation
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(ii) Cl2 + 2e– → 2Cl-

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Reduction
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(iii) Fe → Fe2+ + 2e–

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Oxidation
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(tv) Sn4+ + 2e– → Sn2+

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Reduction

Ans: 6. The minimum oxidation number shown by S is – 2 since it can acquire 2 more
electrons to achieve the nearest inert gas [Ar] configuration.

The maximum Ox. No. shown by S is +6 since it has 6 valance electrons. (3S2 3P4)

Long Answer:
Ans: 1. Various atoms are assigned oxidation number on the basis of the following rules:

(18)
 REDOX REACTIONS
08

1. An element in the free state has an oxidation number equal to zero, e.g. H2, He, K, Ag
all have zero ox. no.

2. In a binary compound of a metal and a non-metal, the oxidation number of metal is

positive while that of non-metal is negative. In NaCl the ox. no. of sodium +1 and ox. n.
of chlorine is -1.

3. In a covalent compound, the atom with higher electronegativity has a negative

oxidation number while another atom has a positive oxidation number.

)
4. The oxidation number of the radical or ions is equal to the electrical charge on it. for

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e.g. the ox. no. of Na+ is +1.

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5. In neutral molecules, the algebraic sum of the oxidation number of all the atoms is zero.

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Ans: 2. The skeletal equation is

a
MnO4–+ H+ + Cl–(aq) → Mn2+ + Cl2(g) + H2O (l) hs
at
Ox. no. of Mn change from +7 in MnO4– to +2
Whereas ox. no. of chlorine changes from -1 in Cl– ions to 0 in Cl2.
lp
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ig
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w
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Ans: 3. The following steps are used for balancing the reactions by this methods:

1. Writing the skeletal equation for all the reactants and products of the reaction.
2. Assignment of the oxidation number of all atoms in each compound in the skeletal
equation. Identify the atoms undergoing a change in their oxidation number.
3. Calculating the increase or decrease in oxidation number per atom and then for the whole
molecule in which it occurs. If these are not equal, then multiplying by suitable
coefficients such that these become equal.
4. Now balancing the chemical reaction with respect to all atoms except H & O.

(19)
 REDOX REACTIONS
08

5. Finally balancing with respect to H & O atom for balancing oxygen atoms add H20
molecules to the side deficient in it.

Ans: 4. (i) OF2

Let the ox. no. of O = x

The ox. no. of each F = — 1

x–2=0

x = +2

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(ii) Na2O2

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Let the o. no. of O = x

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ox. no. of each Na = + 1

a
2 + 2x = 0
hs
at
2x = – 2
lp

x=–1
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(iii) CH3COOH
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Let the ox. no. of O = x

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The ox. no. of each carbon atom = — 1

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The ox. no. of hydrogen = +1

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– 2 + 4 + 2x = 0

2x + 2 = 0

x=–1

Ans: 5. The balanced ionic equation for the reaction is

MnO4– + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O

from the balanced equation, it is evident that-

(20)
 REDOX REACTIONS
08

1 mole of KMnO4 = 5 moles of FeSO4

Applying the molarity equation to the balanced redox equation.

)
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Thus, the volume of M/8 KMnO4 solution required = 10.0 ml.

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Assertion Reason Answer:

a
hs
1. (ii) Both A and R are true but R is not the correct explanation of A.
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2. (iii) A is true but R is false.
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Case Study Answer:

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1. Answer:
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(1) (c) 3
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(2) (b) Evolved

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(3) (b) Stronger reducing agent than H+/ H2 couple

(w

(4) (b) In redox reaction, the oxidation number of oxidant increases, while that of reductant
decreases

2. Answer:

(1) (a)KMnO4
(2) (c) Fluorine
(3) (c) + 6
(4) (b) + 3

(21)
CHEMISTRY
)
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CHAPTER 9: HYDROGEN

a
hs
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lp
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 HYDROGEN
09

HYDROGEN
Introduction

In this chapter we will study the preparation, properties of dihydrogen and of some important
compounds formed by hydrogen like H2O and H2O2.

Hydrogen is the first element of the periodic table. The atomic structure of hydrogen is the
most simplest one with only one proton and one electron. Hydrogen occurs in its atomic form
only at very high temperatures. Water is one of the most important compounds formed by

)
hydrogen. Even its name hydrogen was given by Lavoisier because of its ability to form water as

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in Greek, hydro means water and gene means forming.

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Position of Hydrogen in the Periodic Table

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Hydrogen is the first element in the periodic table. The electronic configuration of hydrogen is
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1s1, yet its position in the periodic table is not certain and unsatisfactory. Hydrogen exhibits
properties similar to both alkali metals (Group 1) and halogens (Group 17).
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Resemblance with Alkali Metals
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Like alkali metals, hydrogen has only one electron in its outer shell.

Alkali metals have a strong tendency to lose one electron from their outermost shell. Similarly,
ig

hydrogen also loses electron to form H+ ion.

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Alkali metals form stable oxides, halides and sulphides. Similarly, hydrogen also forms stable
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oxide (H2O), halides (HF) and sulphide (H2S).

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Resemblance with Halogens

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Halogens have a tendency to gain one electron. Similarly, hydrogen (1s1) gains one electron to
form H- ion.

Hydrogen molecule is diatomic (H2) and so are the molecules of halogens (say F2).

Hydrogen forms hydrides with carbon (e.g., CH4), just like halogens form halides with carbon
(CCl4).

Isotopes of Hydrogen

Isotopes are the different forms of the same element having same atomic number but different
mass numbers. There are three isotopes of hydrogen namely protium, deuterium and tritium.

(1)
 HYDROGEN
09

1. Protium or ordinary hydrogen (1H1): It has one proton and no neutron in the nucleus and
one electron revolves around the nucleus.

2. Deuterium (1H2 or D): It is also known as heavy hydrogen. It has one proton and one neutron
in the nucleus around which one electron revolves.

3. Tritium (1H3 or T): This isotope of hydrogen is radioactive and emits low energy β– particles
having half-life period of 12.33 years. It has one proton and two neutrons in the nucleus. The
concentration of tritium is very low.

Dihydrogen

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Occurrence

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Dihydrogen is the most abundant element in the universe. It constitutes about 70% of the total
mass of the universe. But its abundance in earth’s atmosphere is very less. It is just 0.15% by

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mass in the earth’s atmosphere. In free state hydrogen is present in volcanic gases and in the

a
combined form it constitutes 15.4% of the earth’s crust and the oceans. However, it is also
hs
present in the plant and animal tissues, carbohydrates, proteins etc. Even hydrogen is present
in mineral resources like coal and petroleum.
at
lp

Hydrogen is the principal element in the solar atmosphere. It is present in the outer
atmosphere of Sun and other stars of the universe+ like Jupiter and Saturn.
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Preparation of Dihydrogen
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1. Laboratory Preparation of Dihydrogen

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i. In laboratory dihydrogen is prepared by the reaction of granulated zinc with dilute

hydrochloric acid or dilute sulphuric acid.
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Zn + 2H+(dil) ⟶ Zn2+ + H2

ii. Zinc reacts with aqueous alkali to give dihydrogen

Zn + 2NaOH ⟶ Na2ZnO + H2

2. Commercial Production of Dihydrogen

i. By the electrolysis of water: Electrolysis of acidified water using platinum electrodes is

used for the bulk preparation of hydrogen.

2H2O ⟶ 2H2 + O2

ii. By the action of steam on coke: Dihydrogen is prepared by passing steam over coke or

(2)
 HYDROGEN
09

hydrocarbons at high temperature (1270 K) in the presence of Nickel catalyst.

C + H2O ⟶ CO + H2

The mixture of CO(g) and H2(g) is called water gas. It is also known as synthesis gas or
simply ‘syn gas’ because it is used in the synthesis of methanol and many other
hydrocarbons.

Properties of Dihydrogen

i. Physical Properties

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• Dihydrogen is a colorless, odourless, tasteless, combustible gas.

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• It is lighter than air.

• It is insoluble in water.

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ii. Chemical Properties
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Reaction with halogens: It reacts with halogens, X2 to give hydrogen halides, HX,
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H2 + X2 ⟶ 2HX (X F,Cl, Br,I)
lp

Reaction with dioxygen: It reacts with dioxygen to form water. The reaction is highly
ita

exothermic.
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2H2 + O2 ⟶ 2H2O
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Reaction with dinitrogen: With dinitrogen it forms ammonia.

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3H2 + N2 ⟶ NH3
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Reactions with metals: Dihydrogen reacts with metals to yield hydrides at high
temperature.

H2 + 2M(g) ⟶ 2MH(s)

where M is an alkali metal.

Hydrogenation of vegetable oils: Edible oils (unsaturated) like cotton seed oil, groundnut
oil are converted into solid fat (saturated) also called vegetable ghee by passing hydrogen
through it in the presence of Ni at 473 K.

Vegetable oil + H2 ⟶ Fat

(3)
 HYDROGEN
09

Uses of Dihydrogen

1. Synthesis of ammonia: Dihydrogen is used in Haber’s process in the synthesis of ammonia.

2. Hydrogenation of oils: Dihydrogen is added to oils like soyabean oil, cotton seed oil for
manufacturing vanaspati fat.

3. Manufacture of methyl alcohol: Water gas enriched with hydrogen gas in the presence of
cobalt catalyst gives methanol.

4. Manufacture of hydrogen chloride: It is used in the manufacturing of hydrogen chloride

which is a very important chemical.

)
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5. Manufacture of metal hydrides: It is used in the manufacture of many metal hydrides.

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6. Metallurgical processes: Since, dihydrogen is used to reduce heavy metal oxides to metals,

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as it is a reducing agent. Therefore, it finds its use in metallurgical processes.

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7. Rocket fuel: It is used as a rocket fuel for space research in the form of liquid hydrogen and
liquid oxygen.
hs
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8. Fuel Cells: Dihydrogen is used in fuel cells for the generation of electrical energy.
lp

9. It is used in the atomic hydrogen torch and oxyhydrogen torches for cutting and welding
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purposes.
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Hydrides
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Hydrogen combines with a large number of other elements including metals and non-metals,
except noble gases to form binary compounds called hydrides. If ‘E’ is the symbol of the
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element then hydrides are represented as EHx (e.g., BeH2)

(w

Based on their physical and chemical properties, the hydrides have been classified into three
main categories:

• Ionic or saline or salt like hydrides.

• Covalent or molecular hydrides.

• Metallic or non-stoichiometric hydrides.

Ionic or Saline Hydrides

The ionic hydrides are stoichiometric which are formed when hydrogen combines with

(4)
 HYDROGEN
09

elements of s-block elements except Be. Ionic hydrides are formed by transfer of electrons
from metals to hydrogen atoms and contain hydrogen as H– ion e.g., sodium hydride (Na+H–)

Covalent or Molecular Hydrides

Covalent or molecular hydrides are the compounds of hydrogen with p-block elements. The
most common hydrides are CH4, H2O, NH3 etc. Covalent hydrides are volatile compounds.

Metallic or Non-Stoichiometric Hydrides

The elements of group 3, 4, 5 (d-block) and f-block elements form metallic hydrides. In group
6, only chromium forms hydride (CrH). Metals of group 7, 8, 9 do not form hydrides. These

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hydrides are known as metallic hydrides because they conduct electricity.

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Water

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Water is an oxide of hydrogen. It is an important component of all living organisms. Water

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constitutes about 65% of human body and 95% of plants. It is therefore essential for life. The
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ability of water to dissolve so many other substances makes it a compound of great
importance. Almost three-fourth of the earth’s surface is covered with water.
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lp

Physical Properties of Water

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1. Pure water is colourless, odourless and tasteless.

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2. Water is present in the liquid state at room temperature.

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3. Water boils at 100°C and changes into the gaseous state whereas it freezes at 0°C to form
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ice.
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4. Water molecules undergo extensive hydrogen bonding.

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5. It is an excellent solvent for many thing like alcohols and carbohydrates dissolve in water.

Structure of Water

(5)
 HYDROGEN
09

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Structure of Ice

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Chemical Properties
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1. Amphoteric nature: Water can act both as an acid as well as a base and is thus said to be
an amphoteric substance.
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Water as base: Water acts as a base towards acids stronger than it as shown below,
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H2O + HCl ⟶ H3O+ + Cl-

Water as an acid: Water acts as an acid towards bases stronger than it.

H2O + NH3 ⟶ OH- + NH4+

2. Redox reactions involving water: Water can act both as oxidising as well as reducing
agent.

Oxidising agent: Water acts as an oxidising agent when it gets reduced.

2H2O + 2Na ⟶ 2NaOH + H2

(6)
 HYDROGEN
09

Reducing agent: Water acts as a reducing agent when it gets oxidised.

2H2O + 2F2 ⟶ 4H+ + 4F- + O2

3. Hydrolysis reaction: Water is an excellent solvent due to its high dielectric constant
(78.39). In addition, water can easily hydrolyses many ionic and covalent compounds.

Water hydrolyses oxides and halides of non-metals forming their respective acids

P4O10 + 6H2O ⟶ 4H3PO4

4. Hydrates Formation: From aqueous solutions many salts can be crystallised as hydrated

)
salts. Hydrates are of three types:

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i. Coordinated water

For example: [Ni(H2O)6]2+ (NO3-)2 and [Fe(H2O)6]Cl3

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ii. Interstitial water

For example: BaCl2.2H2O

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iii. Hydrogen bonded water
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For example: [Cu(H2O)4]2+ SO42- H20 in CuS04.5H2O

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Hard and Soft Water

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Hard water is the one which does not produce lather with soap easily due to the presence of
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calcium and magnesium salts in the form of their bicarbonates, chlorides and sulphates. For
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example, sea water etc.

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Soft water is the one which is free from the soluble salts of calcium and magnesium. It gives
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lather with soap easily. For example, distilled water, rain water etc.

Types of Hardness

1. Temporary hardness: It is due to the presence of bicarbonates of calcium and magnesium.

Temporary hardness is called so because it can be easily removed by boiling.

2. Permanent hardness: This type of hardness is due to the presence of chlorides and
sulphates of calcium and magnesium dissolved in water. As this type of hardness cannot be
removed by simple boiling, therefore it is known as permanent hardness.

Softening of Water

(7)
 HYDROGEN
09

The process of removal of hardness from water is called softening of water.

i. Removal of temporary hardness: Temporary hardness can be removed by the following

methods:

a) Boiling: The temporary hardness of water can easily be removed by boiling the water in
large boilers. During boiling the soluble Mg(HCO3)2 is converted into Mg(OH)2 instead of
MgCO3 because Mg(OH)2 is precipitated easily, whereas Ca(HCO3)2 is changed to
insoluble CaCO3 and gets precipitated. These precipitates can be removed by filtration
process. So, the filtrate obtained will be soft water.

)
Mg(HCO3)2 ⟶ Mg(OH)2 + 2CO2

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Ca(HCO3)2 ⟶ Ca(OH)2 + H2O + 2CO2

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b) Clark’s method: In this process the calculated amount of lime is added to hard water

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containing bicarbonates of calcium and magnesium. It precipitates out calcium

a
carbonate and magnesium hydroxide which are then filtered to obtain soft water.

Ca(HCO3)2 + Ca(OH)2 ⟶ 2CaCO3↓ + 2H2O

hs
at
Mg(HCO3)2 + 2Ca(OH)2 ⟶ 2CaCO3↓ + Mg(OH)2↓ + 2H2O
lp

ii. Permanent hardness: Permanent hardness of water is due to the presence of chlorides and
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sulphates of calcium and magnesium. It cannot be removed by simple boiling. So, the
following methods are employed for removing permanent hardness:
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a) Treatment with washing soda: When calculated amount of Na2CO3 (washing soda) is
added to hard water containing soluble sulphates and chlorides of calcium and
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magnesium, then these soluble salts get converted into insoluble carbonates which get
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precipitated.
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CaCl2 + Na2CO3 ⟶ 3CaCO3↓ + 2NaCl

MgSO4 + Na2CO3 ⟶ 3MgCO3↓ + Na2SO4

d) Ion-exchange method: This process employs the use of zeolite or permutit which is
hydrated sodium aluminium silicate (NaAlSiO4), therefore, it is also known as
zeolite/permutit process. For the sake of simplicity sodium aluminium silicate is written as
NaZ. When zeolite is added to hard water, the cations present in hard water are exchanged
for sodium ions.

2NaZ(s) + M2+(aq) ⟶ MZ2(s) + 2Na+(aq) (M = Mg, Ca)

(8)
 HYDROGEN
09

Hydrogen Peroxide

Hydrogen peroxide was discovered by a French chemist J. L. Thenard. It is an important

chemical used in pollution control treatment of domestic and industrial effluents.

Preparation

By the action of sulphuric acid on hydrated barium peroxide

BaO.8H2O + H2SO4 ⟶ BaSO4 + H2O2 + H2O

)
Physical Properties

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1. Pure hydrogen peroxide is a syrupy liquid. It is colourless but gives a bluish tinge in thick

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layers.
2. It is soluble in water, alcohol and ether in all proportions.

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3. It is more viscous than water. This is due to the fact that molecules of H 2O2 are more

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associated through H-bonding. hs
Structure
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Chemical Properties
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a) Oxidising property: Hydrogen peroxide acts as an oxidising agent both in acidic as well as
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in alkaline medium.
H2O2 + 2H+ + 2e- ⟶ 2H2O
b) Reducing Property: In presence of strong oxidising agents, hydrogen peroxide behaves as a
reducing agent in both the medium.
H2O2 + O3 ⟶ H2O + 2O2
c) Decomposition: H2O2 is an unstable liquid
2H2O2 ⟶ 2H2O + O2

Uses
1. In daily life it is used as a material to bleach delicate materials like hair, cotton, wool, silk

(9)
 HYDROGEN
09

etc.
2. It is used as a mild disinfectant. It is also a valuable antiseptic which is sold under the name
of perhydrol.
3. In the manufacture of sodium perborate, sodium percarbonate. These are used in high
quality detergents.
4. In the synthesis of hydroquinone, tartaric acid and certain food products and
pharmaceuticals (cephalosporin) etc.
5. It is used in industries as a bleaching agent for paper pulp, leather, oils, fats and textiles
etc.

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Heavy Water (D2O)

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Method Heavy water is chemically deuterium oxide (D2O). It was discovered by Urey in 1932.

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Preparation

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It is prepared by the exhaustive electrolysis of water. When prolonged electrolysis of water is
done, then H2 is liberated much faster than D2 and the remaining water becomes enriched in
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heavy water.
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H2O + D2 ⟶ D2O + H2
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Uses
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1. Heavy water is used as a moderator in nuclear reactors.

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2. It is used as a tracer compound, in studying the reaction mechanisms.

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3. It is used as a starting material for the preparation of a number of deuterium compounds.

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Hydrogen Economy
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Hydrogen Economy
One proposed way to meet the need for new energy sources is to burn hydrogen as a fuel in
industry and power plants and possibly also in homes and motor. This proposal is referred to
hydrogen economy.
Advantages of hydrogen econom
1) Dihydrogen releases large quantities of heat on combustion. The energy released by
combustion of fuels like dihydrogen, methane, LPG as compared in terms of the same amount
in mole, mass and volume.On mass to mass basis, dihydrogen can release more energy than
gasoline i.e. Octane number is about 3 times.

(10)
 HYDROGEN
09

Energy

released on Dihydrogen (in Dihydrogen (in Octane( in

LPG CH4 gas
combustion gaseous state) liquid state) liquid state)

(in KJ)

per mole 286 285 2220 880 5511

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per gram 143 142 50 53 47

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per litre 12 9968 25590 35 34005

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hs
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2) Burning of hydrogen in air or dioxygen not only liberates large amount of energy but yields
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water as the only product. Burning of hydrogen produces no pollutant like SO2 that are
responsible for acid rain ,nor carbon dioxide that is responsible for the greenhouse effect ,nor
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carcinogenic hydrocarbons nor lead compounds.

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There are two major barriers in achieving the goal of hydrogen economy
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1) To find out a cheap method for large scale production of dihydrogen.

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Two methods which have been proposed are :

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a)Electrolysis of water and the thermochemical reactions cycle. The first method is not
economically viable since the cost of production of dihydrogen by electrolysis of water is so
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high that almost all dihydrogen is obtained from natural gas which itself is in short supply.
b) The other method involves series of thermochemical reactions in which the only things
consumed are water and heat and only products are hydrogen and oxygen while all the other
species are recycled.
2) To find out an effective means of storing dihydrogen.
The gaseous dihydrogen because of its bulk, is difficult to store, but liquid dihydrogen can be
stored relatively easily and safely in cryogenic tanks.
It is also feasible to transport liquid dihydrogen by road or rail tankers of 20000 US gallons
capacity.It can also be stored in underground tanks and transported by pipelines. However it
may not be convenient to store liquid dihydrogen in a home or in a car since the boiling point

(11)
 HYDROGEN
09

of dihydrogen is very low.

Dihydrogen must be kept out of contact with oxygen or air with which it forms explosive
mixture. The only alternative left is to store dihydrogen or metal in an alloy as interstitial
hydride.

Methods to remove hardness

Temporary hardness : It can be removed by following methods :
• Boiling
• Clarks method

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Boiling : In this when we boil hard water, bicarbonates are convereted into hydroxides and
calcium bicarbonate is converted into carbonates. These precipitates are filtered and thus,

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hardness is removed .
Clark’s method: In this method calculated amount of lime is added that precipitates Calcium

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and Magnessium carbonates .

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hs
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Permanent hardness : It is removed by following methods :

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• With washing soda

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• Calgon’s process
• Ion exchange method
• Synthetic resin method
1. With washing soda : In this washing soda is added .It reacts with calcium and
magnessium chlorides and sulphates to form soluble carbonates as shown :

(12)
 HYDROGEN
09

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Ion – exchange method

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In this a substance called zeolite or permutit is added. This zeolite exchange Sodium with
Calcium and Magnessium ions of hard water .

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Example of permutit are many like :hydrated Sodium Aluminium Silicates

a
(Na2Al2Si2O8.xH2O)commonly can be indicated as NaZ .
The apparatus is set as shown :
hs
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lp
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Procedure :
• The zeolite is loosely packed over layers of gravel and sand in big tank .

(13)
 HYDROGEN
09

• Hard water is introduced from top into the base of tank.

• From the bottom water rises up through gravel and sand layers.
• Finally it percolates through the bed of permutit.
• During this the ions are exchanged .
• So ,the water above the permutit layer is generally soft water .

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3.Synthetic Resin Method

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hs
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lp
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Synthetic resin methods are more superior then the ion exchange method as they remove all
types of cations and anions and the resultant water is distilled water .
These resins are generally of two types :
• Cation exchange resin
• Anion exchnage resin
Cation exchange resin : It consist of giant hydrocarbon framework attached to basic groups .
They are represented by general formula R-COOH or R-SO3H .In this R is giant hydrocarbon
.These resins can exchange H+ ions with cations present in hard water .
Anion exchange resin : It consist of giant hydrocarbon frmaework attached to basic groups like

(14)
 HYDROGEN
09

OH- ions, usually in the form of subsituted ammonium hydroxides. They are represented as R-
NH3OH- where R denotes giant hydrocarbon framework .These resins can exchange hydroxide
ion with anions like chloride ions and sulfate ions present in hard water .

Thus the water that comes out from the tank is richer in hydrogen ions,this water is then
passed through second tank ,here the anions are exchanges with hydroxide ion to form

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distilled water.

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4.Calgon process
hs
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In this procss calcium and magnessium ions are rendered ineffective by treatment with
lp

sodium polymetaphosphate . The trade name for it is calgon .when Calgon is added to hard
water the Calcium ,Magnessium ions present in it combine with this Calgon to form soluble
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complex of Calcium and Magnessium salts .

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That is :
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Summary-
1. Hydrogen has the simplest atomic structure with only one proton and one electron. It is
the only element which has no neutron.
2. Hydrogen has properties similar to both alkali metals as well as halogens. Therefore, its
position in the periodic table was not certain and it is best placed separately.
3. There are three isotopes of hydrogen namely protium ( 1H1), deuterium (1H2, D) and
tritium (1H3, T) . The predominant form of hydrogen is protium which has no neutron,
deuterium has one neutron, tritium which is radioactive has two neutrons.
4. Hydrogen in its elemental form exists as dihydrogen. Dihydrogen is the most abundant
element in the universe.

(15)
 HYDROGEN
09

5. ‘Syn gas’ or ‘water gas’ is a mixture of CO and H2.

6. Dihydrogen is colourless, odourless and combustible gas. The H–H bond dissociation
enthalpy is the highest for a single bond between two atoms of any element.
7. The main use of dihydrogen is in the formation of vegetable ghee by hydrogenation of
vegetable oils and also the formation of ammonia by Haber’s process.
8. Atomic hydrogen and oxyhydrogen torches are used for cutting and welding purpose.
9. It acts as a rocket fuel and even has a promising potential for use as a non-polluting fuel
of the near future (hydrogen economy).
10.Hydrogen forms three category of hydrides namely ionic hydrides, covalent hydrides and

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metallic hydrides.

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11.Covalent hydrides are further classified into electron-deficient, electron-precise and
electronrich hydrides based on the relative number of electrons and bonds in their Lewis

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structures.

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12.Water is a substance which is of great chemical and biological significance. It is a solvent
of great importance. hs
13.Water has highest density at 4°C.
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14.Water reacts with large number of substances. It exhibits amphoteric nature.
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15.Water dissolves many salts in it making it hard. Hard water is the one which contains
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calcium and magnesium salts in the form of hydrogencarbonate, chlorides and sulphates.
16.The temporary hardness of water is due to the presence of magnesium and calcium
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hydrogencarbonates which can be removed simply by boiling.

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17.The permanent hardness of water is due to the presence of soluble salts of magnesium
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and calcium in the form of chlorides and sulphates. It is mainly removed by the ion-
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exchange methods.
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18.Hydrogen peroxide has a non-planar open-book like structure. It is a good bleaching

agent and is used in pollution control treatment of industrial and domestic effluents.

(16)
 09
HYDROGEN

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hs
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(17)
 HYDROGEN
09

Important Questions
Multiple Choice questions-
Question 1When water is dropped over sodium peroxide, the colourless gas produced is:
(a) DiNitrogen
(b) DiOxygen
(c) DiHydrogen
(d) Hydrogen Peroxide

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Question 2. The atomic weights of isotopes of all element are different due to different number

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of __________.

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(a) Protons
(b) Electrons

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(c) Neutrons

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(d) None of Above hs
Question 3. During the reaction of natural gas and steam the catalyst used is
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(a) Fe
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(b) Zn
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(c) Ni
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(d) Cr
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Question 4. Cavendish in 766 discovered.

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(a) Nitrogen
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(b) Oxygen
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(c) Hydrogen
(d) Helium
Question 5. Dihydrogen gas may be prepared by heating caustic soda on
(a) Cu
(b) Zn
(c) Na
(d) Ag
Question 6. Hydrogen set free at the time of its preparation from its compound in atomic form
are called _________.

(18)
 HYDROGEN
09

(a) Nascent Molecular Hydrogen

(b) Nascent Atomic Hydride
(c) Both (1) and (2)
(d) Nascent Hydrogen
Question 7. Which substance does not speed up decomposition of H2O2
(a) Glycerol
(b) Pt
(c) Gold

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(d) MnO2

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Question 8. Water shows anomalous behavior between
(a) 0 to 4 °C

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(b) 0 to 5 °C

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(c) 0 to -4 °C hs
(d) 4 to 0 °C
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Question 9. Which of the following pair of substance will not evolve H2 gas?
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(a) Iron and aqueous H2SO4

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(b) Copper and HCl(aq)

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(c) Sodium and Ethanol

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(d) Iron and Steam

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Question 10. Tritium __________ radio active isotope.

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(a) Beta-Emitting
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(b) Alpha – Emitting

(c) Gamma-Emitting
(d) None of the Above
Question 11. The maximum density of water at 40C is:
(a) 1.0 g / cm³
(b) 0.998 g / cm³
(c) 0.918 g / cm³
(d) 1.2 g / dm³
Question 12. Water gas is mixture of hydrogen H2 and

(19)
 HYDROGEN
09

(a) CO
(b) CO2
(c) Cl2
(d) SO2
Question 13. The volume of oxygen gas evolved at STP by decomposition of 0.68 g “20 volume”
hydrogen peroxide is:
(a) 112 ml
(b) 224 ml

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(c) 56 ml

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(d) 336 ml

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Question 14. Which of the following statements regarding hydrogen peroxide is/are incorrect?

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(a) As aerating agent in production of sponge rubber

a
(b) As an antichlor
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(c) For restoring white colour of blackened lead painting
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(d) All of the above
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Question 15. _______ on water decolourises H2O2

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(a) O3
(b) Acidic KMnO4 solution
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(c) Black Suspension of Lead Sulphide( PbS)

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(d) None of these

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Very Short:
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1. Which gaseous compound on treatment with dihydrogen produces methanol?

2. What are the constituents of water gas?
3. Arrange H2, D2, T2 in the decreasing order of their
(i) Boiling point
(ii) Heat of fusion.
4. Which isotope of hydrogen
(i) does not contain neutron
(ii) is radioactive?
5. Out of the following metals which can be used to liberate H2 gas on reaction with dil.

(20)
 HYDROGEN
09

hydrochloric acid?
(i) Cu,
(ii) Zn,
(iii) Iron,
(iv) Silver,
(v) Magnesium
6. Name one compound each of hydrogen in which it exists in:
(i) Positive oxidation state

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(ii) Negative oxidation state.

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7. What is the importance of heavy water in nuclear power generation?
8. State two properties in which hydrogen resembles alkali metals.

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9. Give an example of each anionic and covalent hydride.

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10. Why is H2O2 concentrated at low pressure?
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Short Questions:
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1. Hydrogen forms three types of bonds in its compounds. Describe each type of bonding
using suitable examples.
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2. Name one example of a reaction in which dihydrogen acts as

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(i) an oxidizing agent

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(ii) a reducing agent.

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1
3. The process H2(g) + e– → H– (g) is endothermic (DH = +151 kJ mol-1), yet salt- like
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2
hydrides are known. How do you account for this?
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4. Find the volume strength of 1.6 N H2O2 solution.

5. A sample of hard water is allowed to pass through an anion exchanger. Will it produce
lather with soap easily?
6. Anhydrous Ba02 is not used for preparing H2O2 Why?

Long Questions:
1. (a) Compare atomic hydrogen with nascent hydrogen.
(b) What is (i) active hydrogen
(ii) heavy hydrogen? How are they formed?

(21)
 HYDROGEN
09

2. How is the solution of H2O2 concentrated?

3. What are the different methods used for the softening of hard water? Explain the principle
of each method.
4. Show how hydrogen peroxide can function both as an oxidising and a reducing agent
5. Calculate the percentage strength & strength in g/L of 10 volume hydrogen peroxide
solution.

Assertion Reason Questions:

1. In the following questions, a statement of Assertion (A) followed by a statement of Reason

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(R) is given. Choose the correct option out of the choices given below each question.

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Assertion (A) : Permanent hardness of water is removed by treatment with
washing soda.

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Reason (R) : Washing soda reacts with soluble magnesium and calcium

a
sulphate to form insoluble carbonates. hs
(i) Statements A and R both are correct and R is the correct explanation of A.
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(ii) A is correct but R is not correct.
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(iii) A and R both are correct but R is not the correct explanation of A.
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(iv) A and R both are false.

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2. In the following questions, a statement of Assertion (A) followed by a statement of Reason

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(R) is given. Choose the correct option out of the choices given below each question.
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Assertion (A) : Some metals like platinum and palladium, can be used as
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storage media for hydrogen.

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Reason (R) : Platinum and palladium can absorb large volumes of

hydrogen.
(i) Statements A and R both are correct and R is the correct explanation of A.
(ii) A is correct but R is not correct.
(iii) A and R both are correct but R is not the correct explanation of A.
(iv) A and R both are false.
Case Study Based Question:
1. Read the passage given below and answer the following questions :

(22)
 HYDROGEN
09

Hydrogen can exist in three isotopic forms, viz., protium, deuterium and tritium, which differ
from each other in the number of neutrons.
Out of these three isotopes, tritium is formed in the upper atmosphere by reaction induce
by cosmic rays. It decays to emit low energy β-particles.

Tritium is used for making thermonuclear devices and for carrying out researches in
fusion reactions as a source of energy. It is also used as a radioactive tracer as it is relatively

)
cheap and easy to work with.

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(1) The relative atomic mass of isotopes of hydrogen is:

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(a) 1 : 2 : 3

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(b) 1 : 1 : 2

a
(c) 2 : 4 : 5
(d) 1 : 2 : 4
hs
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(2) The n/ p ratio for 1H2 is:
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(a) 1 : 2
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(b) 1 : 1
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(c) 2 : 1
(d) 2 : 3
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(3) Which is the most reactive isotope of hydrogen?

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(a) Tritium
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(b) Deuterium
(c) Protium
(d) All are equally reactive

(4) What type of reactions are generated by tritium?

(a) Chemical reaction
(b) Radioactive reaction
(c) Addition reaction
(d) All of these

(23)
 HYDROGEN
09

2. Read the passage given below and answer the following questions:

Water is the main constituent of earth’s hydrosphere and fluids of all known living
organisms. It is vital for all known forms of life, even though it provides no chlorines or
organic nutrients.
Water cover approximately 70.9% of earth’s surface, mostly in seas and oceans. Water plays
an important role in the world economy. Approximately 70% of the fresh water used by
humans goes to agriculture. Water is the excellent solvent for a wide variety of substance
both mineral and organic; as such it is widely used in industrial processes and in cooking and
washing. Water, ice and snow are also central to many sports and other forms of

)
entertainment pure water has a low electrical conductivity, which increases with the

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dissolution of a small amount of ionic material such as common salt.

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(1) Which one of the following statements about water is incorrect?

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(a) Water can act both as an acid and as a base

a
(b) Water can be easily reduced to dihydrogen by highly electronegative elements.
hs
(c) Ice formed by heavy water sinks in normal water
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(d) Presence of water can be detected by adding a drop to anhydrous CuSO4
lp

(2) In nuclear reactors, ordinary water is not used as a moderator because

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(a) it cannot slow down the fast moving neutrons

(b) it cannot remove the heat from the reactor core
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(c) it has corrosive action on the metallic parts of the nuclear reactor
.d

(d) None of the above

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(3) Consider the following statements about intermolecular and intramolecular hydrogen
bonding.
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I. Both types of H-bonds are temperature dependent.

II. Water exhibits amphoteric nature.
III. The boiling points of compounds having intramolecular H-bond are lower than
those having intermolecular H-bond.
Which of the statements given above are correct?
(a) I and III
(b) Both II and III
(c) I and II
(d) All of these

(24)
 HYDROGEN
09

(4) Consider the following statements regarding water.

I. There is extensive hydrogen bonding between water molecules .
II. Water has high melting point in comparison to H2S and H2Se.
III. High heat of vaporisation and heat capacity of water are responsible for
moderation of climate and body temperature of living beings.
IV. Covalent compounds like alcohol and carbohydrates dissolve in water.
Select the correct statements among above.
(a) Both I and II

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(b) Both II and IV

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(c) I, II and III

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(d) All of these

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Answer Key:

a
MCQ
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1. (b) DiOxygen
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2. (c) Neutrons
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3. (c) Ni
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4. (c) Hydrogen
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5. (b) Zn
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6. (a) Nascent Molecular Hydrogen

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7. (b) Pt

8. (a) 0 to 4 °C

9. (b) Copper and HCl(aq)

10.(a) Beta-Emitting

11.(a) 1.0 g / cm³

12.(a) CO

13.(b) 224 ml

(25)
 HYDROGEN
09

14.(d) All of the above

15.(c) Black Suspension of Lead Sulphide (PbS)

Very Short Answer:

1. Carbon monoxide (CO).

2. Carbon monoxide and hydrogen.

3. T2 > D2 > H2

)
T2 > D2 > H2.

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4. Protium
Tritium.

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5. Only Zn, Fe, Mg.

a
6. HCl hs
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NaH.
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7. It is used as a moderator in nuclear reactions to slow down the speed of fast-moving

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neutrons.
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8. Both form unipositive ion

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Both have one electron in their s orbital (ns1).

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9. Ionic Hydride NaH Covalent hydride NH3.

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10. Because it decomposes at ordinary pressure or on heating.

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Short Answer:
Ans: 1. Hydrogen forms compounds in three different ways:

1. By loss of electrons as in the reactions of H2 with CuO

2. By gain of electrons as in reactions of H2 with metals.

(26)
 HYDROGEN
09

3. By sharing of electrons as in the reactions of H2 with halogens

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Ans: 2. As an oxidizing agent

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Here Na has been oxidized to Na while dihydrogen has been reduced to H+ ion.
hs
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(ii) a reducing agent.
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Here CuO has been reduced to copper and H2 has been oxidized to H2O.
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.d

Ans: 3. This is due to the reason that high lattice energy released (energy released during the
w

formation of solid metal hydride from their corresponding gaseous ions, i.e., M+ and H+) more
than compensates the energy, needed for the formation of H– ions from H2 gas.
w
(w

Ans: 4. Strength = Normality × EQuestion wt.

Eq. wt.of H2O2 = 17

∴ Strength of 1.6N H2O2 solution = 1.6 × 17g L-1

Now 68g of H2O2 gives 22400 mL O2 at NTP/STP

22400
∴ 1.6 × 17g of H2O2 will give = × 1.6 × 17
68

= 8960 mL of O2 at STP

But 1.6 × 17g of H2O2 are present in 1000 mL of H2O2 solution

(27)
 HYDROGEN
09

Hence 1000 mL of H2O2 solution gives 8960 mL of O2 at STP 1 mL of H2O2 will give = 8.96 mL of
O2 at STP.

Hence the volume strength of 1.6N H2O2 solution is = 8.96 volume

Ans: 5. No. Ca2+ and Mg2+ ions are still present, and these will react with soap to form curdy
white ppt. Therefore, it will not produce lather with soap solution easily.

Ans: 6. BaSO4 formed during the reaction of BaO2 with H2SO4 forms a protective layer around
unreacted BaO2 and the reaction stops after some time.

)
Long Answer:

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Ans: 1. Comparison of atomic and nascent hydrogen

la
The main point of differences are:

a
hs
1. Nascent hydrogen can be produced even at room temperature, but atomic hydrogen is
produced only at very high temperature.
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lp

2. Nascent hydrogen can never be isolated, but atomic hydrogen can be isolated.
ita

3. The reducing power of atomic hydrogen is much greater than that of nascent hydrogen.
ig

In general reactivity of the three forms of hydrogen increases in order.

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Molecular hydrogen (H2) < Nascent hydrogen < Atomic hydrogen.

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Active Hydrogen: It is obtained by subjecting a stream of molecular hydrogen at ordinary

temperature to silent electric discharge at about 30,000 volts. It is very reactive in nature (half-
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life = 0.33 second, and combines directly at ordinary temperatures with Pb and S forming their
hydrides

Heavy hydrogen: It is manufactured by the electrolysis of heavy water containing a little of IT SO,
or NaOH to make the solution conducting.

In the laboratory, it can be prepared by the action of heavy water on sodium metal.

(28)
 HYDROGEN
09

2D2O(l) + 2Na(s) → 2NaOD(aq) + D2(g).

Ans: 2. The concentration of hydrogen peroxide: Hydrogen peroxide obtained by any method is
always in the form of a dilute solution. Great care is to be taken for concentrating its solution
because it is unstable and decomposes on heating.
2H2O2 → 2H2O + O2

The decomposition of H2O2 is catalysed by the ions of heavy metals present as impurities.

The solution of H2O2 is concentrated by the following methods.

)
1. By careful evaporation on a water bath: A dilute solution of H2O2 is taken in a shallow

m
evaporating dish and is heated at 313K – 323 K. Water evaporates slowly and a hydrogen-

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peroxide solution of about 15 – 50% strength is obtained.

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2. By dehydration in a vacuum desiccator: The dilute (50 %) solution of H2O2 obtained as above, is
further concentrated by placing the same in a vacuum desiccator containing concentrated H2SO4

a
as a dehydrating agent. Here, water vapours are absorbed by concentrated sulphuric acid. This is
hs
shown in the diagram
at
lp
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ig
.d
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w

(Concentration of H2O2 in vacuum desiccator)

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3. By distillation under reduced pressure: The solution of hydrogen peroxide is further

concentrated by subjecting it to distillation under reduced pressure. The solution is distilled at
308 – 313 K under a reduced pressure of 15 mm Hg. Water present in the solution distils over
leaving behind about 98 – 99% concentrated solution of hydrogen peroxide.

4. By crystallization: The last traces of water present in H2O are removed by freezing it in a
freezing mixture of solid CO2 and others. The crystals of hydrogen peroxide separate out. These
crystals are removed, dried and then remitted to obtain 100% pure hydrogen peroxide.

5. Storage of hydrogen peroxide: In order to check the decomposition of hydrogen peroxide, a

(29)
 HYDROGEN
09

small amount of acetanilide (i.e. negative catalyst) is added to it before storing the hydrogen
peroxide.

Hydrogen peroxide cannot be concentrated by distillation at ordinary pressure because it

undergoes decomposition into water and oxygen as it is a highly unstable liquid. It decomposes
even on long-standing or on heating.

Ans: 3. Hard water can be softened by the following methods depending upon the nature of
hardness.
(a) Temporary hardness:

)
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1. By boiling: It can be removed by merely boiling the water. Boiling decomposes the

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bicarbonates to give carbon dioxide and insoluble carbonates, which can be removed by
filtration.

a la
hs
at
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2. Clark’s process: Temporary hardness can be removed by the addition of a calculated amount
ita

of lime, whereupon magnesium and/or calcium carbonates is precipitated.

Ca(HCO3)2 + Ca(OH) 2 → 2CaCO3 + 2H2O
ig

Mg(HCO3)2 + Ca(OH) 2 → CaCO33 + MgCO3 + 2H2O

.d

(b) Permanent hardness:

w
w

1. With sodium carbonate: On treatment with washing soda, Ca2+ and Mg2+ in hard water are
(w

precipitated. The precipitate of the insoluble carbonates thus formed is removed by

filtration.

2. Ion-exchange method: The common substance used for this process is zeolite which is
hydrated sodium aluminum silicate, NaAl(SiO)2, The exchange occurs when passing over the
zeolite bed, sodium ions from zeolite are replaced by calcium and magnesium ions. Thus

Na(Ze) + Mg2+ → (Ze)2Ca + 2Na+

(30)
 HYDROGEN
09

2NaZe + Mg2+ → (Ze)2Mg + 2Na+

when all the sodium ions of the zeolite have been replaced, the zeolite is said to be
exhausted. It can be regenerated by treatment with a strong solution of sodium chloride.
2Na + (Ze)2Ca → 2ZeNa + Ca2+.

Ans: 4. Oxidising properties: H2O2 has a tendency to accept electrons in chemical reactions and
thus behaves as an oxidising agent in both acidic and alkaline medium.

H2O2 → H2O + O

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In acidic medium

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H2O2 + 2H+ + 2e– → 2H2O

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In alkaline medium

a
H2O2 + OH– + 2e– → 3OH– hs
at
Example:
lp

(a) In acidic medium:

ita

2Fe2+ + 2H+ + H2O2 → 2Fe3+ + 2H2O

ig

(b) In alkaline medium:

.d

3Cr3+ + 4H2O2 + 100H– → 3CrO42- + 8H2O

w
w

Reducing properties: H2O2 can give electrons in a few reactions and thus behaves as a reducing
agent.
(w

In acidic medium

H2O2 → O2 + 2H+ + 2e–

In alkaline medium

H2O2 + 2OH– → 2H2O + O2 + 2e–

Reducing property in acidic medium:

2MnO42- + 6H+ + 5H2O2 → 2Mn2+ + 8H2O + 5O2

(31)
 HYDROGEN
09

Reducing property in basic medium:

2Fe3+ + H2O2 + 2OH– → 2Fe2+ + O2 + 2H2O

Ans: 5. H2O2 decomposes on heating according to the equation

)
From the equation

m
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22.4L of O2 at N.T.P are obtained from 68g of H202
68

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∴ 10 ml of O2 at N.T.P will be obtained from × 10g of H2O2
22400

a
But 10 ml of O2 at N.T.P are produced from 1 ml. of 10 volume H2O2 solution.
hs
68
at
Thus 1 ml of 10 volume H2O2 solution contains × 10 g of H2O2
22400
lp

∴ 100 ml. of 10 volume H2O2 solution will contain

ita

68 10
× × 100 = 3.036g .
22400 1
ig
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Thus a 10 volume H2O2 solution is approx. 3%

w

Alternatively, 1000 ml of 10 volume of H2O2will contain H2O2

w

68
× 10 × 1000 = 30.36g
(w

22400

Therefore, strength of H2O2 in 10 volume H2O2 is 30.36 g/L

Assertion Reason Answer:

1. (i) Statements A and R both are correct and R is the correct explanation of A.

2. (i) Statements A and R both are correct and R is the correct explanation of A.

Case Study Answer:

1. Answer:

(32)
 HYDROGEN
09

(1) (a) 1 : 2 : 3
(2) (b) 1 : 1
(3) (a) Tritium
(4) (b) Radioactive reaction

2. Answer:

(1) (b) Water can be easily reduced to dihydrogen by highly electronegative elements.
(2) (d) None of the above

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(3) (d) All of these

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(4) (c) I, II and III

a la
hs
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(33)
CHEMISTRY

)
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CHAPTER 10: THE S-BLOCK ELEMENTS

a la
hs
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 THE S-BLOCK ELEMENTS
10

THE S-BLOCK ELEMENTS

Introduction

In the previous chapter we have discussed about The Hydrogen but in this chapter we will study
the general characteristics of the alkali and alkaline earth metals and their compounds. We will
also study the compounds of s-block elements, their uses and importance, commercially and
industrially. The biological significance of sodium, potassium, calcium and magnesium will also
be discussed in this chapter.

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The s-Block Elements

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The s-block elements of the Periodic Table are those in which the last electron enters the

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outermost s-orbital. As the s-orbital can accommodate only two electrons, two groups (1 & 2)
belong to the s-block of the Periodic Table.

a
Group-1 of periodic table contains
hs
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Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Caesium (Cs) and Francium (Fr).
lp

Together these elements are called alkali metals because they form hydroxides on reaction
with water, which are strongly alkaline in nature.
ita

The group-2
ig

Includes Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba) and Radium
.d

(Ra). Except Beryllium, rest of the elements of group-2 are called the alkaline earth metals.
w

These are called so because their oxides and hydroxides are alkaline in nature and these metal
w

oxides are found in the earth crust.

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Group-1 Elements : Alkali Metals

1. Electronic Configuration

Electronic Configuration of elements of group-1 is ns1, where n represents the valence shell.
The alkali metals have one valence electron, outside the noble gas core.

(1)
 THE S-BLOCK ELEMENTS
10

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2. Atomic and ionic radii hs
The atoms of alkali metals have the largest size in their respective periods. The atomic radius
at
increases on moving down the group because on moving down the group there is a progressive
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addition of new energy shells.

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3. Ionization enthalpy
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The ionization enthalpies of the alkali metals are generally low and decrease down the group
from Li to Cs. This is because on moving down the group is due to increase in size of the atoms
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of alkali metals and increase in the magnitude of screening effect.

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4. Hydration enthalpy
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The alkali metal ions are extensively hydrated in aqueous solutions. The hydration enthalpies of
alkali metal ions decrease with increase in ionic size Li+ > Na+ > K+ > Rb+ > Cs+.

5. Physical properties
i. Alkali metals are silvery white in colour and are generally soft and light metals.
ii. The densities of alkali metals are low and increase down the group. Alkali metals have low
melting and boiling point.
iii. When alkali are heated metals they impart characteristic colours to the flame.
iv. When the excited electron comes back to the ground state, there is emission of radiation in
the visible region.

(2)
 THE S-BLOCK ELEMENTS
10

6. Chemical Properties

The alkali metals are highly reactive elements. The cause for their high chemical reactivity is:

i. Low value of first ionisation enthalpy

ii. Large size

iii. low heat of atomisation.

i. Reaction with Air: Alkali metals burn very fast in oxygen and form different kind of oxides
like monoxides, peroxides and superoxides. In all the compounds formed by alkali metals

)
with oxygen, their oxidation state is +1.

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4Li + O2 ⟶ 2Li2O (Oxide)

Na + O2 ⟶ Na2O2 (Peroxide)

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M + O2 ⟶ MO2 (Superoxide)
hs
ii. Reaction with Water: The alkali metals on reaction with water form their respective
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hydroxide and dihydrogen.
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2M + 2H2O ⟶ 2M+ + 2OH- + H2

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(M = an alkali metal)
ig

iii. Reaction with Dihydrogen: Alkali metal react with dry di-hydrogen at about 673K (lithium
.d

at 1073K) to form crystalline hydrides which are ionic in nature and have high melting
points.
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2M + H2 ⟶ 2M+H-
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iv. Reaction with Halogens: The alkali metals react vigorously with halogens and form halides
which are ionic in nature, M+X–. But the halides of lithium are a bit covalent in nature.

v. Reaction with Mercury: The alkali metals have strong tendency to get oxidised, that is why
they act as strong reducing agents, among these lithium is the strongest and sodium is the
least powerful reducing agent.

vi. Reducing Nature: Alkali metals combine with mercury to form amalgams. The reaction is
highly exothermic in nature.

Na + Hg ⟶ Na[Hg]

vii. Solutions in liquid Ammonia: All alkali metals dissolve in liquid ammonia and give deep blue

(3)
 THE S-BLOCK ELEMENTS
10

colour solution which are conducting in nature. These solutions contain ammoniated
cations and ammoniated electrons as shown below:

M + (x + y)NH3 ⟶ [M(NH3)x]+ + [e(NH3)y]–

Uses of Alkali Metals

1. Lithium is used as a metal in a number of alloys. Its alloys with aluminium to make
aircraft parts.
2. Lithium hydroxides is used in the ventilation systems of space crafts and submarines to
absorb carbondioxide.

)
3. Lithium aluminium hydride (LiAlH4) is a powerful reducing agent which is commonly used

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in organic synthesis.

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4. Liquid sodium or its alloys with potassium is used as a coolant in nuclear reactors.

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5. Sodium-lead alloy is used for the preparation of tetraethyl lead, Pb(C2H5)4, which is used
as an antiknocking agent in petrol.

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hs
6. Sodium is used in the production of sodium vapour lamps.
7. Potassium chloride is used as fertilizer.
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8. Potassium hydroxide is used in the manufacture of soft soaps and also as absorbent of
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carbon dioxide.
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9. Potassium ions play a vital role in biological systems.

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10.Caesium is used in photoelectric cells.

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Anomalous Properties of Lithium

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Lithium shows properties which are very different from the other members of its group. This is
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due to the:
1. Exceptionally small size of its atom and ion.
2. Greater polarizing power of lithium ion.
3. As compared to other alkali metals, lithium is harder and its melting point and boiling
point are higher.
4. Among all the alkali metals lithium is least reactive but the strongest reducing agent.

Some important Compounds of Sodium

Sodium is highly reactive and always found in combined state. The isotope of sodium (Na) is

(4)
 THE S-BLOCK ELEMENTS
10

used in detection of leukemia. The compound of sodium are given below:

1. Sodium Oxide (Na2O)

Preparation:

2NaNO2 + 6Na ⟶ 4Na2O + N2

Properties:
1. Sodium oxide is a colourless ionic solid.

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2. Aqueous solution of sodium oxide is strongly basic.

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3. Sodium oxide on reaction with liquid ammonia forms sodamide.
4. At low temperature, when sodium peroxide is reacted with water or acids, H2O2 is

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formed.

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2. Sodium Peroxide (Na2O2) hs
Preparation:
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Sodium when heated in excess of air or when heated in excess of pure oxygen gives sodium
peroxide.
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2Na + O2 ⟶ Na2O2
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Properties:
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1. Sodium peroxide is a pale yellow diamagnetic compound.

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2. Sodium peroxide is a powerful oxidising agent.

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3. Sodium peroxide combines with CO and CO2 to give carbonate.

(w

4. At low temperature, when sodium peroxide is reacted with water or acids, H 2O2 is
formed.
Na2O2 + 2H2O ⟶ 2NaOH + H2O2

3. Sodium Hydroxide (Caustic Soda) (NaOH)

Preparation:

When sodium carbonate is treated with calcium hydroxide it give calcium carbonate along
with sodium hydroxide. Also known as lime caustic soda process. It is a reversible reaction.

Na2CO3 + Ca(OH)2 ⟶ 2NaOH + CaCO3

(5)
 THE S-BLOCK ELEMENTS
10

Properties
1. Sodium hydroxide is a white crystalline deliquescent solid.
2. Sodium hydroxide is corrosive in nature.
3. Sodium hydroxide is highly soluble in water.
4. Sodium hydroxide reacts with acid forming corresponding salts.
NaOH + HCl ⟶ NaCl + H2O

Uses:

)
It is used in the manufacture of soap, paper, artificial silk and a number of chemicals,

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1. In petroleum refining.

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2. In the purification of bauxite.

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3. In the textile industries for mercerising cotton fabrics.

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4. For the preparation of pure fats and oils.
5. As a laboratory reagent.
hs
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4. Sodium Carbonate (Na2CO3)
lp

Preparation:
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NH3 + H2O + CO2 ⟶ NH4HCO3

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NaCl + NH4HCO3 ⟶ NaHCO3 + NH4Cl

.d

2NaHCO3 ⟶ Na2CO3 + H2O + CO2

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Properties:
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1. Sodium carbonate is a white crystalline solid.

2. Na2CO3.10H2O is known as washing soda.
3. Sodium carbonate reacts with acids to give carbon dioxide.

Uses:
1. It is used in water softening, laundering and cleaning.
2. It is used in the manufacture of glass, soap, borax and caustic soda.
3. It is used in paper, paints and textile industries.
4. It is an important laboratory reagent both in qualitative and quantitative analysis.
Na2CO3 + HCl ⟶ NaCl + H2O + CO2

(6)
 THE S-BLOCK ELEMENTS
10

Properties:

On heating sodium bicarbonate loses CO2 and H2O forming Na2CO3.

2NaHCO3 ⟶ Na2CO3 + H2O + CO2

5. Sodium Chloride (NaCl)

Manufacture of sodium chloride is done from sea water. Sea water is allowed to dry up
under summer heat in small tanks and solid crust so formed is collected.

Properties:

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1. Sodium chloride is a white crystalline solid.

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2. It is slightly hygroscopic.
3. It is soluble in water and insoluble in alcohol.

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Uses:

a
hs
1. It is used as a common salt or table salt for domestic purpose.
2. It is used for the preparation of Na2O2, NaOH and Na2CO3.
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6. Sodium Bicarbonate (Baking Soda) (NaHCO3)

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Preparation:
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When NaOH is treated with CO2 in presence of H2O it gives sodium bicarbonate.
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NaOH + CO2 + H2O ⟶ NaHCO3

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Properties:
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On heating sodium bicarbonate loses CO2 and H2O forming Na2CO3.

(w

2NaHCO3 ⟶ Na2CO3 + H2O + CO2

Group-2 Elements : Alkaline Earth Metals

The elements of group-2 are Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr),
Barium (Ba) and Radium (Ra). Except for Be, rest are known as alkaline earth metals, because
they were alkaline in nature and existed in the earth.

1. Electronic Configuration

(7)
 THE S-BLOCK ELEMENTS
10

The alkaline earth metals have 2 electrons in the s-orbital of the valence shell. Their general
electronic configuration [Noble gas]ns2

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a la
hs
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lp
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2. Atomic and Ionic Radii

ig
.d

The atomic radii as well as ionic radii of the members of the family are smaller than the
corresponding members of alkali metals. Within the group, the atomic and ionic radii increase
w

with increase in atomic number.

w

3. Ionization Enthalpies
(w

The alkaline earth metals owing to their large size of atoms have fairly low values of ionization
enthalpies. Within the group, the ionization enthalpy decreases as the atomic number
increases.

4. Hydration Enthalpies

The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metal ions.
Therefore, compounds of alkaline earth metals are more extensively hydrated, for example,
magnesium chloride and calcium chloride exist. the hydration enthalpies of alkaline earth metal
ions decrease with increase in ionic size down the group. Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+

(8)
 THE S-BLOCK ELEMENTS
10

5. Physical Properties

The alkaline earth metals are silvery white, lustrous and relatively soft but harder than the alkali
metals. The melting and boiling points of these metals are higher than the corresponding alkali
metals. The electropositive character increases down the group from Be to Ba, Calcium,
strontium and barium impart characteristic brick red, crimson and apple green colours
respectively to the flame. The alkaline earth metals just like those of alkali metals have high
electrical and thermal conductivities.

6. Chemical Properties

)
As compared to alkali metals, alkaline earth metals are less reactive due to their relatively

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higher ionization enthalpies. The reactivity of alkaline earth metals increases on going down the

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group.

i. Reaction with water: Ca Sr, and Ba have reduction potentials similar to those of

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corresponding group Ist metals and are quite high in the electrochemical series. They react

a
with cold water readily, liberating hydrogen forming metal hydroxides.

Ca + 2H2O ⟶ Ca(OH)2 + H2
hs
at
ii. Reaction with Air: Except Be these metals are easily tarnished in air as a layer of oxide is
lp

formed on their surface. Ba in powdered form bursts into flame on exposure to air.
ita

iii. Reaction with hydrogen: The elements Mg, Ca, Sr and Ba all react with hydrogen to form
ig

hydrides MH2.
.d

iv. Reaction with oxygen: Except Ba and Ra the elements when burnt in oxygen form oxides of
w

the type MO.

w

v. Reaction with halogens: When heated with halogens the alkaline earth metals directly
combine with them and form the halides of the type MX2.
(w

Ca + Cl2 ⟶ CaCl2

vi. Reaction with acids: The alkaline earth metals readily react with acids liberating dihydrogen.

M + 2HCl ⟶ MCl2 + H2

Uses of alkaline earth metals:

1. Beryllium is used in the manufacture of alloys. Cooper-Beryllium alloys are used in the
making of high strength springs.
2. Metallic beryllium is used for making windows of X-rays tubes.

(9)
 THE S-BLOCK ELEMENTS
10

3. Magnesium, being a light metal, forms many light alloys with aluminum, zinc, manganese
and tin.
4. Magnesium is used in flash powders and bulbs, incendiary bombs and signals.
5. Magnesium-aluminium alloys are used in aircraft construction.
6. Magnesium is used as sacrificial anode for the prevention of corrosion of iron.
7. A suspension of magnesium hydroxide in water (called milk of magnesia) is used as an
ant-acid to control excess acidity in stomach.
8. Magnesium carbonate is an ingredient of tooth-paste.

)
9. Calcium is used in the extraction of metals from oxides which are difficult to reduce with

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carbon.

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10.Calcium and barium metals are used to remove air from vacuum tubes, due to their
tendency to react with oxygen and nitrogen at high temperature.

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11.Radium salts are used for radio therapy of cancer.

a
Anomalous Behaviour of Beryllium hs
at
Beryllium shows different behaviour from the rest members of its group and shows diagonal
lp

relationship to aluminium due to reasons discussed below.

ita

1. Beryllium has exceptionally small atomic and ionic sizes and therefore does not compare
well with other members of the group, because of high ionisation enthalpy and small size it
ig

forms compounds which are largely covalent and get easily hydrolysed.
.d

2. Beryllium does not exhibit coordination number more than four as in its valence shell, there
w

are only four orbitals. The remaining members of the group can have a coordination number
of six by making use of d-orbitals.
w

3. The oxides and hydroxide of beryllium unlike the hydroxide of other elements in the group,
(w

are amphoteric in nature.

Compounds of Calcium

1. Calcium Oxide (CaO)

Preparation:

Calcium carbonate when decomposed at 800°C gives calcium oxide.

CaCO3 ⟶ CaO + CO2

(10)
 THE S-BLOCK ELEMENTS
10

Properties:
1. Calcium oxide is also known as ‘Quick lime’ or ‘Burnt lime’, is white amorphous substance.
2. When water is added to lime a hissing sound is produced along with clouds of steam. The
lime forms slaked lime [Ca(OH)2].
3. Calcium oxide reacts with moist chlorine to form bleaching powder.
CaO + Cl2 ⟶ CaOCl2
4. Calcium oxide on reaction with moist HCl gas forms CaCl2.
CaO + 2HCl ⟶ CaCl2 + H2O

)
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2. Calcium Carbonate (CaCO3)

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Preparation:

la
Carbon dioxide when passed through lime water gives calcium carbonate.

a
Ca(OH)2 + CO2 ⟶ CaCO3 + H2O
hs
Properties:
at
1. Calcium carbonate is a white powder insoluble in water.
lp

2. Calcium carbonate dissolves in water in presence of CO2 due to formation of calcium

ita

bicarbonate.
CaCO3 + H2O + CO2 ⟶ Ca(HCO3)2
ig
.d

3. Calcium Chloride (CaCl2)

w

Preparation:
w

Calcium oxide, calcium hydroxide or calcium carbonate when treated with HCl gives calcium
(w

chloride.

CaO + 2HCl ⟶ CaCl2 + H2O

Properties:
1. Calcium chloride is a colourless deliquescent crystalline substance which is soluble in
water as well as in alcohol.
2. Crystals of calcium chloride when strongly heated gives off water of crystallizations.
4. Calcium sulphate (Plaster of Paris)
Preparation:

(11)
 THE S-BLOCK ELEMENTS
10

When Gypsum is heated at about 120° - 130°C, Plaster of Paris is formed.

2CaSO4 + 4H2O ⟶ (CaSO4)2H2O + 3H2O
Properties:
1. It is a white crystalline solid. It is sparingly soluble in water.
2. It becomes anhydrous at about 200°C. Anhydrous form is known as dead burnt plaster.
5. Calcium hydroxide Ca(OH)2
Preparation:
CaO + H2O ⟶ Ca(OH)2

)
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Properties:

.co
1. It gives CaCO3 and Ca(HCO3)2 with CO2
Ca(OH)2 + CO2 ⟶ CaCO3 + H2O

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2. On prolong treatment with CO2 milkiness disappears due to formation of Ca(HCO3)2

a
CaCO3 + H2O + CO2 ⟶ Ca(HCO3)2 hs
Diagonal Relationship of Lithium And Magnesium
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Diagonal Relationship of Lithium with Magnesium
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The main points of similarity :

ita

(1) Both have almost similar electronegativities.

ig

(2) Both Li and Mg are quite hard. They are harder and lighter than other elements in
.d

their respective groups.

w

(3) Both LiOH and Mg(OH)2 are weak bases.

w

(4) Both form ionic nitrides when heated in atmosphere of Nitrogen.

(w

6 Li + N2 → 2 Li3N
3 Mg + N2 → 2 Mg3N2
(5) The hydroxides of both lithium and magnesium decompose upon heating.
2 LiOH → Li2O + H2O
Mg (OH)2 → MgO + H2O
(6) Both lithium and magnesium combine with oxygen to form monooxide while other
members of their respective groups form peroxide and superoxide.
4 Li + O2 → 2 Li2O
2 Mg + O2 → 2 MgO

(12)
 THE S-BLOCK ELEMENTS
10

The Li2O and MgO thus formed do not combine with excess O 2 to form peroxide and
superoxide.
(7) The carbonates of these metals decompose on heating to the corresponding oxides
with the evolution of carbon dioxide.
Li2CO3 → Li2O + CO2
MgCO3 → MgO + CO2
(8) Both Lithium and magnesium do not form solid bicarbonates.
(9) Both Lithium and magnesium nitrate decompose on heating producing nitrogen
dioxide.

)
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4 LiNO3 → 2 Li2O + 4 NO2 + O2

.co
2 Mg (NO3) 2 → MgO + 4 NO2 + O2
(10) The hydroxides, carbonate, oxalates, phosphates and fluorides of both Lithium and

la
magnesium are sparingly soluble in water.

a
(11) Because of the covalent character, LiCl and MgCl2 are soluble in ethanol.
hs
(12) Both Lithium perchlorate and magnesium perchlorate are highly soluble in ethanol.
at
(13) LiCl and MgCl2 are deliquescent and crystallise from aqueous solution as hydrate
lp

LiCl·2 H2O and MgCl2 ·6 H2O.

ita

Extraction of Alkali Metals

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Alkali metals cannot be extracted from their ores by the usual methods of extraction of
metals because of following difficulties:
.d

1) Alkali metals are strong reducing agents and hence cannot be extracted by reduction
w

of their oxides or chlorides.

w

2) Alkali metals being highly electropositive cannot be displaced from the aqueous
(w

solution of their salts by other metals.

3) Alkali metals cannot be isolated by electrolysis of the aqueous solution of their salts
since hydrogen is liberated at the cathode instead of the alkali metal because the
standard electrode potentials of alkali metals are much lower than that of water. By
using mercury as cathode ,the alkali metals can be deposited at the cathode but the alkali
metals so deposited readily combines with mercury to form an amalgam from which its
recovery is very difficult.
Extraction of Lithium
Lithium is prepared by electrolysis of fused mixture of dry lithium chloride and potassium
chloride at 723 k.

(13)
 THE S-BLOCK ELEMENTS
10

Potassium chloride is added to increase the conductivity of lithium chloride and also to
lower the fusion temperature. The cell is operated at a temperature of about 723 K and
current voltage of 8-9 V.
As a result of electrolysis, the following reactions takes place:
LiCl ⇔ Li+ + Cl‾
At cathode: Li+ + e‾ ——-> Li
At anode: 2 Cl‾ – 2e‾ —–> Cl2
The metal thus obtained is 99% pure and is stored by keeping it wrapped in paraffin wax.
Lithium being the lightest metal known cannot be stored in kerosene oil since it floats on

)
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the surface.

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Uses of Lithium
1) It is used in the manufacture of alloys

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a) Lithium – lead alloy or white metal which is used for making toughened bearing for

a
motor engines and sheats for cables.
hs
b) Lithium aluminium alloy has great tensile strength and electricity like that of mild
at
steel. It is used for aircraft construction.
lp

c) Lithium magnesium alloy is extremely tough and corrosion resistant which is used for
armour plate and aerospace components.
ita

2) It is used for producing thermonuclear energy required for propelling rockets and
guided missiles.
ig

3) Lithium is used to make both primary and secondary batteries.

.d

4) Lithium is used as a Scavenger since it combines readily with oxygen and nitrogen.
w

Thus it is used for removing little traces of oxygen and nitrogen during refining of metals.
w

5) lithium carbonate is used in making a special variety of glass which is very strong and is
(w

weather proof.
6) Lithium chloride is used in Air conditioning plants to regulate the humidity. It is also
used in Ni-Fe accumulators.
7) Lithium Bromide is used in medicine as sedative.
8) Lithium bicarbonate and lithium salicylate have been used for treatment of
rheumatism since the resulting Lithium urinate is soluble in water.
9) Lithium hydride is used as source of hydrogen for meterological purpose and for filling
of balloons.
10) Lithium Hydroxide is used for removing carbon dioxide from exhaled air in closed
quarters.

(14)
 THE S-BLOCK ELEMENTS
10

11) Lithium aluminium hydride is used as a reducing agent in synthetic organic chemistry.
Extraction of Sodium

)
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a la
hs
Sodium is extracted by the electrolysis of fused sodium chloride by a process called
at
Down’s process.
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Sodium is now obtained by electrolysis of a fused eutectic mixture of sodium chloride

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and calcium chloride in Down’s cell at 873 K using graphite anode and iron cathodes.
As a result of electrolysis ,sodium is liberated at the cathode and Cl 2 is evolved at the
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anode.
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NaCl ——–> Na+ + Cl‾

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At cathode: Na+ + e‾ ———> Na

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At anode: Cl‾ ———-> Cl + e‾

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Cl + Cl ——-> Cl2
Uses of Sodium
1) Sodium is used as a reducing agent in the extraction of boron and silicon.
2) Sodium is employed as a reducing agent in form of sodium amalgam and as a reagent
in Wurtz reaction and in the synthesis of many organic compound.
3) It is also used to make tetraethyl lead,tetra methyl lead which are used as anti
knocking agent for gasoline.
4) liquid Na or its alloys with potassium is used as a coolant in fast breeder nuclear
reactor.

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 THE S-BLOCK ELEMENTS
10

5) It is used in the manufacture of number of chemicals such as Na2O2, NaCN, NaNH2.

6) It is used in sodium vapour lamp.
7) Sodium is largely used in industry for the production of artificial rubber , dyes, drugs.
8) Because of its lightness and high thermal conductivity, it is used for filling exhaust
valves of aeroplane engines.
Use of Potassium
1) It has a vital role in biological system.
2) KCl is used as fertilizer.

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3) KOH is used in manufacture of soap.

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4) It is also used as an excellent absorbent for Carbon dioxide.

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Baking Soda and Sodium Chloride

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Sodium chloride (NaCl)

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The most abundant source of sodium chloride is sea water which contains 2.7 - 2.9% by
mass.
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Common salt is generally obtained by evaporation of sea water. Crude sodium chloride
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obtained by crystallisation of brine solution contains impurities of sodium sulphate

(Na2SO4), calcium sulphate (CaSO4), calcium chloride (CaCl2) magnesium chloride (MgCl2).
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Since MgCl2 and CaCl2 are deliquescent (absorb moisture easily from the atmosphere),
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therefore , impure common salt gets wet in rainy season. To obtain pure sodium chloride
, the crude salt is dissolved in minimum amount of water and filtered to remove insoluble
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impurities. The solution is then saturated with HCl gas when crystals of pure sodium
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chloride separates out. The solution is then saturated with hydrogen chloride gas when
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crystals of pure sodium chloride separates out. The calcium and magnesium chloride
being more soluble remains in the solution.
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Properties
1) Sodium chloride melts at 1081 K.
2) Its solubility is 3.6 g per 100 g of H2O at 273 K. The solubility does not increase
appreciably with rise in temperature.
Uses
1) It is used as a common salt for domestic purpose.
2) It is used in the preparation of Na2CO3, NaOH, Na2O2.
Baking soda or Sodium hydrogen carbonate (NaHCO3)
Sodium hydrogen carbonate is commonly called Baking soda because on heating it

(16)
 THE S-BLOCK ELEMENTS
10

decomposes to evolve bubbles of carbon dioxide.

Preparation
It is prepared by saturating a solution of sodium carbonate with carbon dioxide. Being
less soluble, white crystalline powder of sodium hydrogen carbonate gets separated.
Na2CO3 + CO2 + H2O ———> 2 NaHCO3
Uses
1) It is used in fire extinguishers for generating CO2.
NaHCO3 + HCl ————-> NaCl + CO2 + H2O

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2) It is used in the preparation of baking powder which is a mixture of NaHCO3, starch,

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calcium dihydrogen phosphate Ca(H2PO4), sodium Aluminium Sulphate NaAl (SO4)2.

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3) It is a mild antiseptic for skin infections.

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4) It is used as an antacid in making digestive powders for removing acidity of stomach.

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Cement hs
Cement is essentially a finely powdered mixture of calcium silicate and aluminates along
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with small quantities of gypsum which sets into a hard stone like mass when treated with
water.
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Average composition of Portland cement

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Cement is obtained by combining a material rich in lime, CaO with other materials such
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as clay, which contains silica, SiO2 along with oxides of aluminium, iron and magnesium.
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Lime (CaO) 50 - 60%

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Magnesium oxide (MgO) 2 - 3%

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Silica (SiO2) 20 - 25%

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Ferric oxide (Fe2O3) 1 - 2%

Alumina (Al2O3) 5 - 10%
Sulphur trioxide (SO3) 1 - 2%
For a good quality cement, the ratio of alumina to silica should lie between 2.5 to 4 while
that of lime to that of silica ,alumina and ferric oxide should be as close to 2 as possible.
Raw material
Raw materials required for the manufacture of cement are 1) limestone (CaCO3) ,2) clay
which provides both silica and Alumina 3) gypsum. Small amount of magnesia and iron
oxide are also required for imparting suitable colour to cement.
Manufacture of cement

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 THE S-BLOCK ELEMENTS
10

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Cement is manufactured by two processes:

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(1) Wet process

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(2) Dry process

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The wet process is preferred when the raw materials i.e. limestone and clay are soft,
climate is humid and fuel is cheap. The dry process is preferred when the raw materials
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are hard.
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The main raw materials are limestone and clay. Wet process supplies lime while the dry
process is a source of silica , alumina and iron oxides.
(1) The raw materials are first crushed separately in a suitable machine. They are then
mixed in the required proportion( 3 parts limestone + 1 part clay) and grounded together
finely.This grinding is done either by the dry process or by the wet process.
(2) In the wet process ,the clay is washed with water in a wash mill to remove flint and
other foreign substances. It is then mixed with requisite quantity of limestone and
pulverised in a special mill.The resulting pasty mass is then throughly homogenised to get
raw slurry containing about 40% water.
(3) In the dry process, the raw materials are dried and mixed in desired proportion. The

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 THE S-BLOCK ELEMENTS
10

mixture is then finely powdered and passed through 300 mesh sieves and homogenised
with the help of compressed air. The homogeneous mass is called raw meal.
(4) The slurry or raw meal is introduced into the upper end of a rotary kiln by means of
screw conveyer. The kiln consist of an inclined steel rotating cylinder, 150-200 ft long and
about 10 ft diameter lined inside with fire bricks. The charge travel downwards slowly
due to the rotatory motion given to the kiln and is heated by burning coal dust which is
blown in front from the lower end. The charge takes about 2-3 hours to cover the entire
journey in the kiln.
The following changes occur :

)
(1) In the upper part of the kiln, the temperature is around 1000-1100K .Here the charge

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loses all its water due to evaporation by hot gases.

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(2) In the middle of the kiln, temperature is around 1100-1200 K. Here limestone
decomposes to form calcium oxide and carbon dioxide.

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CaCOW ——–> CaO + CO2

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(3) The lower part of the kiln, from where coal dust is blown in is the hottest with the
hs
temperature ranging between 1770-1870 K. As the charge reaches here ,chemical
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combination takes place between lime, alumina and silica to form calcium silicate and
aluminates.
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2 CaO + SiO2 —> 2 CaO.SiO2

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3 CaO + SiO2 ———> 3 CaO.SiO2

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3 CaO + Al2O3 ——> 3 CaO.Al2O3

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2 CaO + Al2O3 ——> 2 CaO.Al2O3

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4 CaO + Al2O3 + Fe2O3 ——-> 4 CaO. Al2O3.Fe2O3

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Due to very high temperature in this zone, about 20-30 % combines with solid mass to
form grey coloured balls called cements clinkers.
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The hot clinkers are cooled by cold air and are mixed with 2-3 % gypsum and finely
powdered to 325 mesh size in grinding machine. The fine powder called the Portland
cement is sieved and packed in bags.
Setting of cement
The important constituents present in Portland cement are dicalcium silicate (Ca2SiO4),
tricalcium silicate (Ca3SiO5) and tricalcium aluminate (Ca3Al2O6).
When water is added to cement, an exothermic reaction occurs. During this process,
cement reacts with water to form a gelatinous mass which slowly sets into a hard mass
having three dimensional network structure involving -Si-O-Si- and -Si-O-Al chains.

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 THE S-BLOCK ELEMENTS
10

Tricalcium silicate sets quickly and develops considerable strength within a few days.
Dicalcium silicate sets slowly and develops appreciable strength after a month or so.
Tricalcium aluminate sets instantaneously in presence of water. The internal strength
acquired by cement is primarily due to the setting of tricalcium aluminate.

Summary-
1. s-block elements: The elements in which last electron enters into s-orbital are called s-
block elements.

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2. Alkali metals: The elements of group 1 whose hydroxide are strong alkali.

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3. Alkaline earth metal: The elements of group 2, and their oxides and hydroxides are

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alkaline in nature and their oxides are found in the Earth’s crust.
4. Diagonal relationship: The resemblance in properties of elements of second period with

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elements of third period present diagonally on the right hand side.

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5. Monovalent sodium and potassium ions and divalent magnesium and calcium ions are
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found in large proportions in biological fluids. These ions perform important biological
functions such as maintenance of ion balance and nerve impulse conduction.
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 THE S-BLOCK ELEMENTS
10

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 THE S-BLOCK ELEMENTS
10

Important Questions

Multiple Choice questions-

Question 1. Beryllium shows diagonal relationship with
(a) Mg
(b) Na
(c) Al

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(d) B.

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Question 2. Which of the following metal has stable carbonates?

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(a) Na

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(b) Mg

a
(c) Al
(d) Si
hs
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Question 3. The reaction of Cl2 with X gives bleaching powder X is
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(a) CaO
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(b) Ca(OH)2
(c) Ca(OCl)2
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(d) Ca(O3Cl)2
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Question 4. NaOH is prepared by the method

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(a) Downs cell

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(b) Castner cell

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(c) Solvay process

(d) Castner – Kellner cell.
Question 5. Milk of lime reacts with chlorine to form ________, a constituent of bleaching
powder.
(a) Ca(OCI) 2
(b) Ca(CIO2) 2
(c) Ca(CIO3) 2
(d) Ca(CIO4) 2
Question 6. Which one of these are main components of kidney stones?

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 THE S-BLOCK ELEMENTS
10

(a) Sodium Oxalate

(b) Potassium Oxalate
(c) Calcium Oxalate
(d) Copper Oxalate
Question 7. A nitrate of an alkali metal M on heating gives O2.NO2 and M2O. The metal M will
be:
(a) Na
(b) K

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(c) Rb

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(d) Li

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Question 8. Which of the following metal carbonates decompose on heating?

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(a) LiCO3 & MgCO3

a
(b) Na2CO3
(c) K2CO3
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(d) None of the Above
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Question 9. Which of the following alkaline earth metals do not impart any color to the flame?
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(a) Ca,Sr
(b) Mg,Ca
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(c) Be,Mg
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(d) Sr,Ba
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Question 10. Which one of the following alkali metals emit light of longest wavelength in the
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flame test?
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(a) Na
(b) K
(c) Cs
(d) Li
Question 11. What will be final weight of 286 gm Na2CO3.10H2O by Heating at 373 K?
(a) 206 gm
(b) 162 gm
(c) 186 gm
(d) 124 gm

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 THE S-BLOCK ELEMENTS
10

Question 12. Solubilities of carbonates decrease down the magnesium group due to decrease
in
(a) Entropy of solution formation
(b) Lattice energies of solids
(c) Hydration energy of cations
(d) Inter – ionic attraction.
Question 13. What are the products formed when Li2CO3 undergoes decomposition?
(a) Li2O2, CO

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(b) Li2O, CO

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(c) Li2O, CO2

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(d) LiO2, CO

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Question 14. Alkali metals give a _________ when dissolved in liquid ammonia

a
(a) Deep blue solution
(b) Colorless
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(c) Red colour
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(d) None of the Above

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Question 15. _______ does not exhibit coordination number more than four.
(a) Magnesium
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(b) Beryllium
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(c) Calcium
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(d) None of the Above

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Very Short:
1. Which element is found in chlorophyll?
2. Name the elements (alkali metals) which form superoxide when heated in excess of air.
3. Why is the oxidation state of Na and K always + 1?
4. Name the metal which floats on the water without any apparent reaction with water.
5. Why do group 1 elements have the lowest ionisation enthalpy?
6. Why does the following reaction
7. Amongst Li, Na, K, Rb, Cs, Fr which one has the highest and which one has the lowest
ionisation enthalpy?

(24)
 THE S-BLOCK ELEMENTS
10

8. What is the general electronic configuration of alkali metals in their outermost shells?
9. What is meant by dead burnt plaster?
10. Name three forms of calcium carbonate.

Short Questions:
1. Why the solubility of alkaline metal hydroxides increases down the group?
2. Why the solubility of alkaline earth metal carbonates and sulphates decreases down the
group?

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3. Why cannot potassium carbonate be prepared by the SOLVAY process?

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4. What are the main uses of calcium and magnesium?

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5. What is meant by the diagonal relationship in the periodic table? What is it due to?

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6. Why is the density of potassium less than that of sodium?

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Long Questions: hs
1. Why is it that the s-block elements never occur in a free state? What are their usual
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modes of occurrence?
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2. Explain what happens when:

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(a) Sodium hydrogen carbonate is heated.

(b) Sodium with Mercury reacts with water.
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3. What is the effect of heat on the following compounds?

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(a) Calcium carbonate

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(b) Magnesium chloride hexahydrate

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(c) Gypsum
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4. State as to why
(a) An aqueous solution of sodium carbonate gives an alkaline test.
(b) Sodium is prepared by electrolytic method & not by chemical method.
(c) Lithium on being heated in the air mainly forms mono-oxide & not the peroxides.
5. What raw materials are used for making cement? Describe the manufacture of Portland
cement. What is its approximate composition?

Assertion Reason Questions:

1. In the following questions, a statement of Assertion (A) followed by a statement of Reason

(25)
 THE S-BLOCK ELEMENTS
10

(R) is given. Choose the correct option out of the choices given below each question.

Assertion (A): The carbonate of lithium decomposes easily on heating to

form lithium oxide and CO2.
Reason (R) : Lithium being very small in size polarises large carbonate
ion leading to the formation of more stable Li2O and CO2.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct

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(iv) A is not correct but R is correct.

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2. In the following questions, a statement of Assertion (A) followed by a statement of Reason
(R) is given. Choose the correct option out of the choices given below each question.

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Assertion (A): Beryllium carbonate is kept in the atmosphere of carbon dioxide.
hs
Reason (R) : Beryllium carbonate is unstable and decomposes to give
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beryllium oxide and carbon dioxide.
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(i) Both A and R are correct and R is the correct explanation of A.

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(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
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(iv) A is not correct but R is correct.

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Case Study Based Question:

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1. Alkali metals have the lowest ionization energy in their corresponding period in periodic
w

table because they have large size which results in a large distance between the nucleus
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and the outermost electron. Ionization energy of alkali metals decreases from Li to Cs due
to increase in atomic size. First ionization energy of alkali metals is very low but they have
very high value of second ionization energy.

(26)
 THE S-BLOCK ELEMENTS
10

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hs
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(1) Alkali metals are characterised by:
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(a) Good conductors of heat and electricity

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(b) High melting points

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(c) Low oxidation potentials

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(d) High ionisaiton potentials.

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(2) Metals dissolve in liquid ammonia giving coloured solutions which are conducting in
nature. The colour of the solution and reason of its conductance is:
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(a) Yellow, NH4+

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(b) Blue, ammoniated metals

(c) Orange, [M(NH3)x]+
(d) Blue, ammoniated electron
(3) Alkali metals displace hydrogen from water forming bases due to the reason that:
(a) They are far above the hydrogen in electrochemical series based on oxidation
potential.
(b) They are far below the hydrogen in electrochemical series based on oxidation
potential.
(c) Their ionization potential is less than that of other elements.

(27)
 THE S-BLOCK ELEMENTS
10

(d) They contain only one electron in their outermost shell.

2. All alkali metals dissolve and form blue solution in liquid ammonia. When alkali metals are
dissolved in liquid ammonia, there is a considerable expansion in total volume hence such
solutions are called expanded metals. The blue solution of an alkali metal in ammonia
shows certain characteristic properties which are explained on the basis of formation of
ammoniated (solvated) metal cations and ammoniated electrons in the metal ammonia
solution in the following way :

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The blue solution is paramagnetic and has high electrical conductivity due to the presence
of unpaired electron in the cavities in ammoniacal solution.
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(1) Sodium dissolves in liquid NH3 to give a deep blue solution. This is due to:
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(a) Ammoniated Na+

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(b) Ammoniated Na–

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(c) Formation of Na+/Na– pair

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(d) Ammoniated electrons.

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(2) The increasing order of the density of alkali metals is:

(a) Li < K < Na < Rb < Cs
(b) Li < Na < K < Rb < Cs
(c) Cs < Rb < Na < K < Li
(d) Cs < Rb < K < Na < Li
(3) The reaction between sodium and water can be made less vigorous by:
(a) Lowering the temperature
(b) Adding a little alcohol

(28)
 THE S-BLOCK ELEMENTS
10

(c) Amalgamating sodium

(d) Adding a little acetic acid.

Answer Key:
MCQ
1. (c) Al

2. (a) Na

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3. (c) Ca(OCl)2

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4. (d) Castner – Kellner cell.

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5. (a) Ca(OCI)2

a
6. (c) Calcium Oxalate
hs
7. (d) Li
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8. (a) LiCO3 & MgCO3
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9. (b) Mg,Ca

10.(b) K
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11.(d) 124 gm
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12.(c) Hydration energy of cations

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13.(c) Li2O, CO2

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14.(a) Deep blue solution

15.(b) Beryllium

Very Short Answer:

1. Magnesium

2. Potassium, rubidium and caesium.

3. It is due to their high second ionisation enthalpy and stability of their ions [Na+, K+].

(29)
 THE S-BLOCK ELEMENTS
10

4. Lithium floats on the water without any apparent reaction to it.

5. Because of the largest size in their respective periods, solitary electron present in the
valence shell can be removed by supplying a small amount of energy.

6. Because larger K+ cation stabilizes larger anion.

7. Li has the highest and Fr has the lowest ionisation enthalpy.

8. ns1 where n = 2 to 7.
9. It is anhydrous calcium sulphate (CaS04).

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10. Limestone, chalk, marble.

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Short Answer:

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Ans: 1. If the anion and the cation are of comparable size, the cationic radius ‘vill influence the

a
lattice energy. Since lattice energy decreases much more than the hydration energy with
hs
increasing ionic size, solubility will increase as we go down the group. This is the case of
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alkaline earth metal hydroxides.
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Ans: 2. If the anion is large compared to the cation, the lattice; energy will remain almost
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constant within a particular group. Since the hydration energies decrease down the group,
solubility will decrease as found for alkaline earth metal carbonates and sulphates.
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Ans: 3. If the anion is large compared to the cation, the lattice; energy will remain almost
constant within a particular group. Since the hydration energies decrease down the group,
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solubility will decrease as found for alkaline earth metal carbonates and sulphates.
w

Ans: 4. Main uses of calcium:

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1. Calcium is used in the extraction of metals from oxides which are difficult to reduce
with carbon.

2. Calcium, due to its affinity for O2 and N2 at elevated temperatures, has often been used
to remove air from vacuum tubes.

Main uses of Magnesium:

1. Magnesium forms alloys with Al, Zn, Mn and Sn. Mg-Al alloys being light in mass are
used in aircraft construction.

(30)
 THE S-BLOCK ELEMENTS
10

2. Magnesium (powder and ribbon) is used in flashbulbs, powders incendiary bombs and
signals.

3. A suspension of Mg (OH)2 in water is used as an antacid in medicine.

4. Magnesium carbonate is an ingredient of toothpaste.

Ans: 5. It has been observed that some elements of the second period show similarities with
the elements of the third period situated diagonally to each other, though belonging to
different groups. This is called a diagonal relationship.

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The cause of the diagonal relationship is due to the similarities in properties such as
electronegativity, ionisation energy, size etc. between the diagonal elements. For example, on
at
moving from left to right across a period, the electronegativity increases, which on moving
lp

down a group, electronegativity decreases. Therefore, on moving diagonally, two opposing

tendencies almost cancel out and the electronegativity values remain almost the same as we
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move diagonally.
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Ans: 6. Generally, in a group density increases with the atomic number, but potassium is an
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exception. It is due to the reason that the atomic volume of K is nearly twice Na, but its mass
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(39) is not exactly double of Na (23). Thus the density of potassium is less than that of sodium.
w

Long Answer:
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Ans: 1. The elements belonging to s-block in the periodic table. These metals (Alkali & alkaline
earth metals) are highly reactive because of their low ionization energy. They are highly
electropositive forming positive ions. So, they are never found in a free state. They are widely
distributed in nature in a combined state. They occur in the earth’s crust in the form of oxides,
chlorides, silicates & carbonates.

Ans: 2. Sodium hydrogen carbonate on heating decomposes to sodium carbonate.

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 THE S-BLOCK ELEMENTS
10

When sodium with mercury reacts with water. It produces sodium hydroxide.

Ans: 3.

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Ans: 4. Sodium carbonate gets hydrolise by water to form an alkaline solution.

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CO32- + H2O → HCO3– + OH

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Due to this, it gives an alkaline test.

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Sodium is a very strong reducing agent. Therefore, it cannot be isolated by a general reduction
hs
of its oxides or other compounds. The metal formed by electrolysis will immediately react
at
with water forming hydroxides. So, sodium is prepared by the electrolytic method only.
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Lithium is the least reactive but the strongest reducing agent of all the alkali metals. It combines
with air, it forms mono-oxide only because it does not react with excess air.
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Ans: 5. Raw materials: The raw materials required for the manufacture of cement are limestone,
stone and clay, limestone in calcium carbonate, CaCO3 and it provides calcium oxide, CaO. Clay-
is a hydrated aluminum silicate, Al2O3 2Si02.2H20 and it provides alumina as well as silica. A
small amount of gypsum, CaS04.2H20 is also required. It is added in calculated quantity in order
to adjust the rate of setting of cement.

Manufacture: Cement is made by strongly heating a mixture of limestone and clay in a rotatory
kiln. Limestone and clay are finely powdered, and a little water is added to get a thick paste
called slurry. The slurry is led into a rotatory kiln from the top through the hopper.

The hot gases produce a temperature of about 1770-1870 K in the kiln. At this high
temperature, the limestone and clay present in the slurry combine to form cement in the form

(32)
 THE S-BLOCK ELEMENTS
10

of small pieces called clinker. This clinker is mixed with 2 – 3 % by weight of gypsum (CaSO4
.2H2O) to regulate the setting time and is then ground to an exceedingly fine powder.

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Manufacture of cement
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When mixed with water the cement reacts to form a gelatinous mass which sets to a hard
mass when three-dimensional cross-links are formed between

…………..Si — O — Si……… and …….. Si — O — Al…… chains.

Composition of cement:

CaO = 50 – 60%

SiO2 = 20 – 25%

Al2O3 = 5 – 10%

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 THE S-BLOCK ELEMENTS
10

MgO = 2 – 3%

Fe2O3 = 1 – 2%

SO3 = 1 – 2%

For a good quality cement, the ratio of silica (SiO2) and alumina (Al2O3) should be between 2.5
to 4.0. Similarly, the ratio of lime (CaO) to the total oxide mixtures consisting of SiO2, Al2O3 and
Fe2O3 should be roughly 2: 1. If lime is in excess, the cement cracks during setting. On the
other hand, if lime is less than required, the cement is weak in strength. Therefore, the proper
composition of cement must be maintained to get cement of good quality.

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Assertion Reason Answer:

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1. (i) Both A and R are correct and R is the correct explanation of A.

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2. (i) Both A and R are correct and R is the correct explanation of A.

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Case Study Answer:
hs
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1. Answer:
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(1) (a) Good conductors of heat and electricity

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(2) (d) Blue, ammoniated electron

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(3) (b) They are far below the hydrogen in electrochemical series based on oxidation
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potential.
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2. Answer:
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(1) (d) Ammoniated electrons

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(2) (a) Li < K < Na < Rb < Cs

(3) (c) Amalgamating sodium.

(34)
CHEMISTRY

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CHAPTER 11: THE P-BLOCK ELEMENTS

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 THE P-BLOCK ELEMENTS
11

THE P-BLOCK ELEMENTS

Introduction

The elements in which last electron enters into p-subshell are called as p-block elements. The
number of p-orbitals is three and, therefore, the maximum number of electrons that can be
accommodated in a set of p-orbitals is six, hence p-block contains six groups.

Boron Family

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Group III A contains six elements: Boron, aluminium, gallium, indium, thallium and ununtrium.

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The penultimate shell (next to the outermost) conains 1s2 in boron, 2s2 2p6 (8 electrons) in
aluminium and (n–1)s2(n–1)p6(n–1)d10 (18 electrons) in other elements.

a la
Boron is a non-metal and always form covalent bonds. Boron family is known as most
hs
heterogeneous family as there is no regular trend in all properties, as it comes after d-block,
lanthanoid contraction, poor shielding of d-orbital, they have large deviation in properties.
at
1. Physical Properties
lp

The atomic radius, ionic radius and density increases when one moves from top to bottom in a
ita

group in periodic table. While melting point decreases from B to Ga and then increases from
(Ga to In). Ionisation energy decreases from B to Al, but shows a reverse trend in going from Al
ig

to Ga.
.d

2. Chemical Properties
w
w

i. Reaction with air: Impure boron in air forms oxide while pure boron is less reactive.
(w

4B + 3O2 ⟶ 2B2O3

ii. Reaction with water: Boron is not affected by water or steam under ordinary conditions.
However, Aluminium reacts with cold water if oxide layer is not present on its surface.

4Tl + 2H2O + O2 ⟶ 4TlOH

iii. Reaction with acids: Boron is not affected by non-oxidising acids like HCl and dilute H2SO4
while other elements dissolve and liberate H2 gas.

2Al + 6HCl ⟶ 2AlCl3 + 3H2

iv. Reaction with alkalies: Boron, Aluminium, Gallium react with alkali solutions whereas

(1)
 THE P-BLOCK ELEMENTS
11

Indium and Thallium are not affected by alkalies.

2B + 6NaOH ⟶ 2Na2BO3 + 3H2

Anomalous Properties of Boron

Boron, the first member of group 13 elements, shows anomalous behaviour and differ from
rest of the members of its family. The main reason for this difference are:
• Exceptionally small atomic and ionic size.

)
m
• High ionization enthalpy.
• Absence of d orbital in its valence shell.

.co
• It has higher melting and boiling point than those of the other members of its group.

a la
Borax hs
It Borax contains the tetranuclear unit i.e. [B4O5(OH)4]2–. The correct formula is Na2
at
[B4O5(OH)4].8H2O.
lp
ita
ig
.d
w
w
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1) From Tincal

Naturally occurring borax is called tincal or suhaga. Tincal obtained from dried up lakes contains
50% borax. It is boiled with water and filtered to remove insoluble impurities of clay ,sand. The
filtrate is concentrated when crystals of borax separate out.

(2)
 THE P-BLOCK ELEMENTS
11

2) From Colemanite

The mineral colemanite is finely powdered and is boiled with sodium carbonate solution.

Ca2B6O11 + 2 Na2CO3 ——–> Na2B4O7 + 2 NaBO2 + 2 CaCO3 ↓

The precipitate of calcium carbonate thus formed is removed by filtration. The filtrate is
concentrated and cooled when crystals of borax separate out. Sodium metaborate present in
the mother liquor can be converted into borax by passing a current of carbon dioxide through
it.

3) From Boric Acid

)
m
Borax can also be prepared in small amounts by neutralising boric acid with sodium carbonate.

.co
On cooling crystal of borax i.e. Na2B4O7.10H2O separate out.

la
Properties of Borax

a
hs
1) It is a white crystalline solid, less soluble in cold water but more soluble in hot water.
at
2) The aqueous solution of borax is alkaline due to hydrolysis. Borax is therefore, used as a
water softener and cleaning agent.
lp
ita

Na2B4O7 + 2 H2O ———-> 2 NaOH + H2B4O7

H2B4O7 + 5 H2O ———-> 4 H3BO3

ig
.d

Action of heat- borax Bead Test

w

Borax loses its water of crystallisation and swells up to form a puffy mass. On further heating ,
w

it melts into a clear liquid which solidifies to a transparent glass like bead which consists of
sodium metaborate (NaBO2) and boric anhydride(B2O3)
(w

Na2B4O7.10H2O ————–> Na2B4O7 + 10 H2O

Na2B4O7 ————-> 2 NaBO2 + B2O3

The glassy bead is commonly known as borax bead and is employed in qualitative analysis for
the detection of certain coloured basic radicals such as Ni2+, Co2+, Cr3+, Cu2+, Mn2+. Whenever a
coloured salt containing these cations is heated with borax bead on a platinum wire, the salt
decomposes to form the corresponding metal oxide which then combines with B 2O3 present in
the glassy bead to form coloured metaborates. This test is called borax bead test.

CoSO4 ———> CoO + SO3

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 THE P-BLOCK ELEMENTS
11

CoO + B2O3 ——> Co (BO2)2

NiO + B2O3 ———-> Ni(BO2)2

Cr2O3 + B2O3 ———-> 2 Cr(BO2)3

MnO + B2O3 ———-> Mn(BO2)2

CuO + B2O3 ———-> Cu(BO2)2

Action of Sodium Hydroxide

)
On adding a calculated quantity of sodium hydroxide to borax , sodium metaborate is formed.

m
Na2B4O7 + 2 NaOH ———–> Na2BO2 + H2O

.co
Action of Sulphuric Acid

la
On adding a calculated quantity of concentrated sulphuric acid to a hot concentrated solution

a
of borax, boric acid is produced. hs
Na2B4O7 + H2SO4 ———> Na2SO4 + H2B4O7
at
lp

H2B4O7 + 5 H2O ——-> 4 H3BO3

ita

Action of Ethyl Alcohol and Sulphuric Acid

ig

On heating borax with ethyl alcohol and concentrated sulphuric acid , vapours of
triethylborates are produced. When ignited these vapours burn with a green edged flame.
.d
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Na2B4O7 + H2SO4 + 5 H2O ———-> Na2SO4 + 4 H2BO3

w

H3BO3 + 3 C2H5OH ——-> B (OC2H5)3 + 3 H2O

(w

Uses of Borax

Borax is used in:

1) in the manufacture of enamels and glazes for earthen ware. The glazed surface is resistant to
heat ,stains and scratches.

2) as a flux in soldering

3) in the preparation of medicinal soaps due to its antiseptic properties.

4) in the manufacture of heat resistant Borosilicate glass.

(4)
 THE P-BLOCK ELEMENTS
11

5) to make peroxoborate- an important cleansing and bleaching agent present in washing

powder.

6) as a stiffening agent for candle wicks.

7) to produce a good finish in laboratory.

8) in the laboratory for borax bead test.

9) in softening of water.

Boron Hydrides

)
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The binary compounds of boron with hydrogen are called Boron hydrides.

.co
These hydrides of boron are called boranes.These hydrides can be divided into several series:

la
1) BnHn+4 (called nido borane) such as B2H6 (diborane), B5H9 (pentaborane) , B6H10 (hexaborane) ,

a
B8H12 (octaborane) , B10H14 (decaborane).
hs
2) BnHn+6 (called arachno borane) such as B4H10 (tetraborane) , B5H9 (pentaborane), B6H10
at
(hexaborane), B8H14 ( octaborane), B9H15 ( nonaborane).
lp

Preparation
ita

1) By reduction of boron trifluoride etherate with Lithium aluminium hydride in diethyl ether.
ig

4 BF3.Et2O + 3 LiAlH4 ——> 2 B2H6 + 3 LiF + 3 AlF3 + 4 Et2O

.d

2) Diborane is prepared in the laboratory by the oxidation of sodium borohydride with iodine in
w

diglyme as solvent.
w

NaBH4 + I2 ———-> B2H6 + 6 NaF

(w

3) On the industrial scale, diborane is obtained by the reduction of BF3 with sodium hydride.

BF3 + 6 NaH ——–> B2H6 + 6 NaF

Preparation of higher boranes

Higher boranes are obtained when B2H6 is heated at 373-523 K.

Properties

1) Physical state

Diborane is a colourless ,highly toxic gas, b.p. 180 K.

(5)
 THE P-BLOCK ELEMENTS
11

2) Stability

Diborane is stable only at low temperature. When diborane is heated in a sealed tube,
between 373- 533 K, a complex reaction occurs and various higher boranes are formed.

B2H6 ——-> B4H10, B5H11, B6H12

By careful control of temperature ,pressure and reaction time , different individual boranes can
be obtained.

2 B2H6 ——> B4H10 + H2

)
3) Combustibility

m
.co
It catches fire spontaneously upon exposure to air. It burns in oxygen evolving an enormous
amount of heat.

la
B2H6 + 3 O2 ——–> B2O3 + 3 H2O ; ΔcH° = -1976 KJ/mol

a
hs
Like diboranes, higher boranes spontaneously burn in air.
at
4) Hydrolysis
lp

Boranes are readily hydrolysed by water to form boric acid.

ita

B2H6 + 6 H2O ——> 2 H3BO3 + 6 H2

ig

With methanol ,trimethylborate is formed.

.d

B2H6 + 6 CH3OH —–> 2 B (OCH3)3 + 6 H2

w

5) Reaction with Lewis bases – cleavage reaction

w
(w

Diborane on treatment with Lewis bases first undergoes cleavage to form borane which then
reacts with Lewis bases to form adducts.

B2H6 + 2 NMe3 ——> 2 BH3.NMe3

B2H6 + 2 CO —> 2 BH3.CO

6) Reaction with Ammonia

(6)
 THE P-BLOCK ELEMENTS
11

)
m
.co
a la
hs
at
lp
ita
ig
.d
w
w
(w

Diborane combines with ammonia to form an addition product, B2H6.2NH3 formulated as

[BH2(NH3)2] + [BH4]‾, which when heated to 473 K decompose to give a volatile compound
called borazine or borazole.

3 B2H6 + 6 NH3 ——–> 3 [BH2 (NH3)2]+ [BH4]‾ ——–> 2 B3N3H6 + 12 H2

Borazine is isoelectronic and isosteric with benzene and its structure is similar to that of
benzene expect that in benzene the π-electrons are completely delocalised but in borazine,
they are only partially delocalized.

Because of its similarity with benzene , borazine is also called inorganic benzene.

7) Formation of complex borohydride

(7)
 THE P-BLOCK ELEMENTS
11

Several metal hydrides react with diborane to from tetrahydridoborates known as borohydride.
All these contain the tetrahedral [BH4]‾ ion.

2 NaH + B2H6 ——> 2 Na+ [BH4]‾

2LiH + B2H6 ——> 2 Li+ [BH4] ‾

Both sodium borohydride and lithium borohydride are used as reducing agent in organic
synthesis. They also serve as starting material for many other borohydrides.

8) Reaction with alkalies

)
Diborane dissolves in strong alkali to produce metaborates and dihydrogen gas.

m
.co
B2H6 + 2 KOH + 2 H2O ——–> 2 KBO2 + 6 H2

9) Action of halogen acids

a la
Diborane reacts with halogen acids to give halodiboranes evolving H2 gas.
hs
The reactivity of halogen acids follow the order: HI> HBr > HCl
at
Thus HI react at about 323 K in absence of catalyst while HBr and HCl reacts in presence of their
lp

aluminium halide as catalyst.

ita

B2H6 + HI ——> B2H5I + H2

ig

B2H6 + HBr ——> B2H5Br + H2

.d

B2H6 + HCl ——> B2H5Cl + H2

w

10) Action of halogens

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(w

Halogens also react with diborane to form the corresponding halodiboranes.

The reactivity decreases in the order: Cl2 > Br2 > I2.

Thus Cl2 reacts explosively at room temperature, Br2 reacts rapidly at 373 K while I 2 reacts
slowly at still higher temperature.

B2H6 + Cl2 ——->B2H5Cl + HCl

Uses of Boron Hydrides

1) Dibornae is used for preparing a number of boron hydrides such as LiBH4 , NaBH4 .

2) It is used as a reducing agent in organic reactions.

(8)
 THE P-BLOCK ELEMENTS
11

3)It is used as a fuel for supersonic rockets.

Structure of Diborane

1) In diborane, each boron atom has 3 Valence electrons for sharing. If we assume that each
boron forms 3 covalent bonds with 3 hydrogen atoms, then there are no electrons left with
boron atom for sharing with other boron atoms. Therefore the two boron atoms cannot be
linked.

There are two types of hydrogen atom :

1) The four hydrogen atoms (two on left and two on right shown by thick lines) are called

)
m
terminal hydrogens.

.co
These four terminal hydrogens and the two boron atoms lie in the same plane while the
remaining two hydrogen atoms- one lying above and one lying below this plane form bridges

la
and hence are called which bridged hydrogen.

a
bana are two types of bonds in B2H6 molecules. hs
1) The four terminal B-H bonds are normal covalent bonds and hence are quite strong. Each
at
bond is formed by sharing a pair of electron between B and H and hence are also called two
lp

centre electron pair bonds or two centre two electron bond (2c - 2e)
ita

2) The two bridge bonds i.e. B—–H—–B are quite different from normal covalent bonds. Each
bridge hydrogen is bonded to two boron atoms by a pair of of electrons. These are three centre
ig

electron pair bonds or three centre 2 electron bonds and hence are quiet weak.
.d

Because of their semblance to a banana, these three centre electron pair bonds are also called
w

banana Bond.
w

Structure of diborane on the basis of hybridization

(w

(9)
 THE P-BLOCK ELEMENTS
11

)
m
.co
a la
hs
at
The boron atom in the excited state is 1s2 2s1 2px1 2py1 2pz0 .
lp

It undergoes sp3 hybridisation

ita

The two half filled hybrid orbitals of each boron atom overlap with the half filled orbitals of
hydrogen atom forming normal covalent bonds whereas the third half filled hybrid orbital of
ig

one boron atom and the vacant hybrid orbital of the second boron atoms overlap
.d

simultaneously with the half filled orbitals of hydrogen atom The electron cloud contains only
w

two electrons but spreads over 3 atoms. That is why this bond is called three centre electron
pair bond.
w
(w

Because of the shape of the electron cloud formed, it is called banana bond. Molecules like
B2H6 which do not have sufficient number of electrons to form normal covalent bonds are
called electron deficient molecules.

Compounds of Boron

1. Borax/ Sodium Tetraborate (Na2B4O7·10H2O)

It is the most important compound of boron. It is a white crystalline solid. Borax dissolves in
water to give an alkaline solution.

Preparation:

(10)
 THE P-BLOCK ELEMENTS
11

From Boric acid: Boric acid is neutralised with sodium carbonate and the resulting solution is
cooled to get crystals of borax.

H3BO3 + Na2CO3 ⟶ Na2B4O7 + H2O + CO2

Properties:

i. It gets hydrolysed with water to form an alkaline solution

Na2B4O7 + 7H2O ⟶ 2NaOH + H3BO3

ii. Borax bead test: On heating borax first swells up due to elimination of water molecules.

)
On further heating it melts to a liquid which then solidifies to a transparent glassy mass.

m
.co
Na2B4O7.10H2O ⟶ Na2B4O7 + 10H2O

Na2B4O7 ⟶ 2NaBO2 + B2O3

a la
iii. It is a useful primary standard for titration against acids.
hs
Na2[B4O5(OH)4]·8H2O + 2HCl ⟶ 2NaCl + 4H3BO3 + 5H2O
at
2. Diborane: B2H6
lp

The simplest boron hydride known, is diborane. It is prepared by treating boron trifluoride
ita

with LiAlH4 in diethyl ether.

ig

Preparation
.d

3LiAlH4 + 4BCl3 ⟶ 3LiCl + 3AlCl3 + B2H6

w

Properties
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i. Stable at low temperature only, colourless and highly toxic.

(w

ii. B2H6 + 6H2O ⟶ 2H3BO3 + 6H2

iii. B2H6 + 6Cl2 ⟶ 2BCl3 + 6HCl
iv. B3H6 + 2Me3N ⟶ 2[Me3N.BH3]

Uses of Boron and Aluminium and Their Compounds

Boron Compounds
Boron is a hard solid having high melting point low density and very low electrical conductivity.
Some important boron compounds are:

(11)
 THE P-BLOCK ELEMENTS
11

1. Boron fibers: It is mixed with plastic to form a material which is lighter than aluminium but
tougher and stiffer than steel hence it is used in body armour, missiles and aircrafts.
2. Boron-10 (10B) isotope: Boron carbide rods or boron steel are used to control nuclear
reactions as neutron absorbers.
10
5B + 0n1 ⟶ 5B11
3. Borax: It is used in manufacture of enamels and glazes for pottery and tiles. It is also used in
making optical glasses and also borosilicate glasses which is very resistant to heat and shock.
It is used as an antispectic.
4. Boric acid: It is used in glass industry, in food industry as preservative. It is also used as an

)
antiseptic and eye wash under the name ‘boric lotion’. It is also used in manufacture of

m
enamels and glazes for pottery.

.co
5. Boron carbide: Hardest boron compound.

la
Aluminium Compounds

a
Aluminium and its alloy are used in packing industry, utensil industry, aeroplane and
transportation industry etc.
hs
at
1. Alumina (Al2O3):
lp

a) Used in chromatography.
b) Used in making bauxite bricks which are used for lining furnaces.
ita

2. Aluminium chloride (AlCl3): Used in manufacture of dyes, drugs and perfumes and also in
ig

manufacture of gasoline. It is also used as catalyst in Friedel Craft reaction.

.d

3. Potash Alum. [K2SO4-Al2(SO4)3-24 H2O]: Used in purification of water, leather tanning, as

antiseptic and as a mordant.
w
w

Group 14 Elements : The Carbon Family

(w

Group IV A contains six elements: carbon, silicon, germanium, tin, lead and ununquadium. The
penultimate shell (prior to outermost) contains 1s2 -grouping in carbon, 2s22p6 (8 electrons) in
silicon and (n–1)s2(n–1)p6(n–1)d10 (18 electrons) in other elements. This shows why carbon
differs from silicon in some respects and these two differ from rest of the members of this
group. General electronic configuration is ns2np2.

1. Atomic and Physical Properties

The important properties of carbon family are discussed below:
i. Atomic Radii: The atomic radii of group 14 elements are less than the corresponding
elements of group 13. However, the atomic radii increases down the family.

(12)
 THE P-BLOCK ELEMENTS
11

ii. Ionisation Energies: The higher ionisation energies than group 13 are due to the higher
nuclear charge and smaller size of atoms of group 14 elements. While moving down the
group, the ionisation energies decreases till Sn.
C > Si > Ge > Sn < Pb
iii. Oxidation state and valency: The elements of group 14 show tetravalency by sharing four
of its valence electrons. Therefore, they have oxidation state of +4. In addition, Ge, Sn and
Pb also show +2 oxidation state.
iv. Catenation: Catenation is ability of like atoms to link with one another through covalent
bonds. Tendency decreases from C to Pb. It is due to the decreasing M-M single bond

)
energy. Thus, the tendency for catenation decreases as:

m
C > Si > Ge > Sn > Pb

.co
v. Allotropy: All the elements of the carbon family with the exception of lead exhibit allotropy.
Carbon exists as two important allotropic forms diamond and graphite.

a la
2. Chemical Properties
hs
i. Reactivity towards air: All members of this group form monoxide of the general formula
at
MO such as CO, SiO, SnO and PbO. All members of this group form dioxides of molecular
formula MO2 such as CO2, SiO2, GeO2, SnO2 and PbO2.
lp

ii. Reactivity towards water: In this family three members i.e., carbon, silicon and germanium
ita

are affected by water while lead is not affected by water due to formation of protective
oxide film, but tin decomposes with steam into tin dioxide and hydrogen gas.
ig

iii. Reactivity towards halogen: These elements form two types of hallides - MX2 and MX4.
.d

Most of the MX4 are covalent. SnF4 and PbF4 are ionic in nature.
w
w

Anomalous Behaviour of Carbon

(w

Carbon shows anomalous behaviour due to its smaller size, higher electronegativity, higher
ionization enthalpy and unavailability of d orbitals. Carbon atom forms double or triple bonds
involving pπ-pπ bonding. Carbon has also the property to form closed chain compounds with O,
S and N atoms as well as forming pπ-pπ multiple bonds with other elements particularly N, S
and O. When we move down the group size increases and electronegativity decreases hence
catenation tendency decreases. Order is:

C >> Si > Ge ≈ S

Allotropes of Carbon

(13)
 THE P-BLOCK ELEMENTS
11

Carbon shows allotropism due to catenation and pπ-pπ bond formation. Carbon exists in two
allotropic forms – crystalline and amorphous. The crystalline forms are diamond and graphite
while the amorphous forms are coal, charcoal and lamp-black. The third form is fullerenes
discovered by Kroto, Smalley and Curl.

Note: Tin has maximum number of allotropes.

Diamond

In diamond each carbon is joined to other four carbon tetrahedrally and carbon-carbon bond
length is 1.54Å and bond angle is 109˚28′ having sp3 hybridisation on each carbon. All four

)
electrons in carbon are involved in bonding hence, it is bad conductor of electricity. Diamond is

m
an excellent thermal conductor.

.co
a la
hs
at
lp
ita
ig

It is hardest natural substance known. It is transparent and has a specific gravity 3.52 and its
.d

refractive index is high (2.45). Difficult to break due to extented covalent bonding. Diamond is
w

used for making cutters. Blades of diamond are used in eye surgery and as an abrasive for
sharpening hard tools. Impure diamonds (black) are used in knives for cutting glass.
w
(w

Graphite

Each carbon is sp2 hybridised. It has layered structure. These layers are attracted by van der
Waals force. Each carbon has one free electron in p-orbital, so it is a good conductor of
electricity. All electrons get delocalized in one layer and form π-bond. Electron jumps from one
orbital to another hence it is a good conductor of heat and electricity. In graphite carbon-
carbon bond length is 141.5 pm and distance between adjacent graphite layer is 340 pm.

(14)
 THE P-BLOCK ELEMENTS
11

)
m
.co
la
Graphite is used as a lubricant at high temperature. Oil gets burn or denatured at high

a
temperature but graphite does not get denatured even at high temperature so, preferred over
oil and grease.
hs
at
Fullerene
lp

It was made as a result of action of a laser beam or strong heating of a sample of graphite in
ita

presence of inert atmosphere. The sooty material mainly contains C60 with C70 (small amount).
Most common fullerene is C60 called Buckminsterfullerene which has football-like structure. It
ig

contains 20 six-membered ring and 12 five-membered ring. It is used to make ball bearings.
.d
w
w
(w

Coal
It is the crude form of carbon. It has been formed in nature as a result of slow decomposition of
vegetable matter under the influence of heat, pressure and limited supply of air. The successive

(15)
 THE P-BLOCK ELEMENTS
11

stages of transformation are peat, lignite, bituminous, steam coal and anthracite. Bituminous is
hard stone, burns with smoky flame. The superior quality is anthracite which burns with non-
smoky flame.
Uses of carbon
• Graphite: In making lead pencils, electrodes of electric furnances, as a moderator in nuclear
reactor, as a lubricant in machinery.
• Charcoal: In removing offensive odour from air, in removing fused oil from crude spirit, in
decolourising sugar syrup, in gas masks etc.

)
• Carbon black: For making printing inks, black paints, Indian inks, boot polishes and ribbons

m
of typewriters.

.co
• Coal: For the manufacture of coal gas, coal tar, coke, and synthetic petrol.

la
Allotropes of Carbon

a
1. Carbon Monoxide (CO)
hs
Preparation: Carbon monoxide is majorly prepared by
at
2C + O2 ⟶ 2CO
lp

Properties:
ita

i. Burns with blue flame

2CO + O2 ⟶ 2CO2
ig

ii. CO + Cl2 ⟶ COCl2 (Phosgene)

.d

iii. CO + 2H2 ⟶ CH3OH

w

iv. Many of the transition metals form metal carbonyls

w

Ni + 4CO ⟶ Ni(CO)4
(w

2. Carbon Dioxide (CO2)

Preparation:
Carbon dioxide is mostly prepared by decomposition of carbonates and bicarbonates:
i. CaCO3 + 2HCl ⟶ CaCl2 + H2O + CO2
ii. CaCO3 ⟶ CaO + CO2
Properties:
Carbon dioxide is an acidic, colourless gas. The important properties are:
i. Zn + CO2 ⟶ ZnO + CO

(16)
 THE P-BLOCK ELEMENTS
11

ii. 2Mg + CO2 ⟶ 2MgO + C

iii. 2NaOH + CO2 ⟶ Na2CO3 + H2O
iv. Na2CO3 + H2O + CO2 ⟶ 2NaHCO3

Silicones
Silicones are synthetic organosilicon polymers containing repeated R2SiO units held by
Si-O-Si linkages.
These compounds have general formula (R2SiO)n where R = methyl or aryl group.

)
Preparation

m
.co
When methyl chloride reacts with silicon in the presence of copper as a catalyst at 570
K , various types of methyl substituted chlorosilanes of formula CH 3SiCl3 , (CH3)2SiCl2,
(CH3)3SiCl along with small amount of (CH3)4Si are formed.

a la
Hydrolysis of dichlorodimethylsilanes followed by polymerization yields chain polymers.
hs
at
lp
ita
ig
.d
w
w
(w

Properties

1) Silicones made up of short chain molecules are oily liquid, silicones with medium
chains behave as viscous oils, jellies and greases, those with very long chains behave
as rubbery elastomers and resins.
2) They are chemically inert i.e. resistant to oxidation , thermal decomposition or to
attack by organic reagents.

(17)
 THE P-BLOCK ELEMENTS
11

3) Silicones being surrounded by non-polar alkyl group are water repelling in nature.

4) They are heat resistant and have high dielectric strength i.e. have good electrical
insulating properties.

Uses

1) For making water proof papers , wool , textile , wood by coating them with a thin film
of silicone.

2) As sealants and electrical insulators.

)
3) As lubricant at high as well as low temperature since there is little change in their

m
viscosities with temperature.

.co
4) Being biocompatible, they are used in surgical and cosmetic implants.

la
Summary-

a
hs
1. Allotropes: Those compounds which have different physical properties but similar chemical
properties are called allotropes e.g., diamond and graphite.
at
2. Catenation: Tendency of carbon atom to link with itself to form long chain is called
lp

catenation.
ita

3. Inert pair effect: Decrease in tendency of ns2 electron pair to participate in bond formation
with increase in atomic number is called inert pair effect.
ig

4. Silicones: It is organosilicon compound containing repeated R2SiO units.

.d

5. Silicates: Compounds in which anions are either discrete SiO4-4 units or a number of such
w

units combine together through corners.

w

6. Alums: All double sulphates having one monovalent basic radical and one trivalent basic
radical.
(w

7. Boranes: Hydrides of boron are called as boranes.

(18)
 THE P-BLOCK ELEMENTS
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 THE P-BLOCK ELEMENTS
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Important Questions
Multiple Choice questions-
Question 1. Consider the following statement about Ozone I. O3 is formed by the interaction of
fluorine. II. It turns tetramethyl base paper as violet. III. It turns benzidine paper as brown. The
correct set of true statement is
(a) I and II
(b) I, II and III
(c) I and III

)
(d) II and III

m
Question 2. In the compound of type ECl3, where E = B, P, As, or Bi, the angle Cl – E – Cl for

.co
different E are ion the order:
(a) B = P = As = Bi

la
(b) B > P > As > Bi

a
(c) B < P = As = Bi
(d) B < P < As < Bi hs
Question 3. In white phosphorous(P4) molecule, which one is not correct:
at
(a) 6P-P single bonds are present
lp

(b) 4P-P single bonds are present

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(c) 4 lone pair of electrons is present

(d) P-P-P bond angle is 60°
ig

Question 4. All the elements of oxygen family are

.d

(a) Non metals

w

(b) Metalloids
w

(c) Radioactive
(d) Polymorphic
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Question 5. Which of the following will not produce hydrogen gas?

(a) Reaction between Fe and dil. HCl
(b) Reaction between Zn and NaOH
(c) Reaction between Zn and conc. H2SO4
(d) Electrolysis of NaCl in Nelsons cell
Question 6. Amorphous form of Silica is
(a) Tridymite
(b) Kieselguhr
(c) Cristobalite
(d) Quartz

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 THE P-BLOCK ELEMENTS
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Question 7. Graphite is a soft solid lubricant extremely difficult to melt. The reason for this
anomalous behavior is that graphite.
(a) Has carbon atoms arranged in large plates of rings of strongly bound carbon atoms with
weak interpolate bonds
(b) Is a non – crystalline substance
(c) Is an allotropic from of carbon
(d) Has molecules of variable molecular masses like polymers.
Question 8. Borax is used as a cleansing agent because on dissolving in water, it gives
(a) Alkaline solution

)
(b) Acidic solution

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(c) Bleaching solution

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(d) Amphoteric solution.
Question 9. Among the C-X bond (where, X = Cl, Br, I) the correct decreasing order of bond

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energy is

a
(a) C−I > C−Cl > C−Br
(b) C−I > C−Br > C−Cl
hs
(c) C−Cl > C−Br > C−I
at
(d) C−Br > C−Cl > C−I
lp

Question 10. On heating boron with caustic potash, the pair of products formed are
ita

(a) Potassium Borate + Dihydrogen

(b) Potassium Borate + Water
ig

(c) Potassium Borate + H2

.d

(d) Borax + Dihydrogen.

w

Question 11. Which of the following statements regarding ozone is not correct?
w

(a) The oxygen-oxygen bond length in ozone is identical with that of molecular oxygen
(b) The ozone is response hybrid of two structures
(w

(c) The ozone molecule is angular in shape

(d) Ozone is used as a germicide and disinfectant for the purification of air.
Question 12. There is no S-S bond in
(a) S2O2-4
(b) S2O2-5
(c) S2O2-3
(d) S2O2-7
Question 13. Which is strongest Lewis acid?
(a) BF3
(b) BCl3

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 THE P-BLOCK ELEMENTS
11

(c) BBr3
(d) BI3
Question 14. Fertilizer having the highest nitrogen percentage is:
(a) Calcium cyanamide
(b) Urea
(c) Ammonium nitrate
(d) Ammonium sulphate
Question 15. In general, the Boron Trihaides act as
(a) Strong reducing agent

)
(b) Lewis Acids

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(c) Lewis Bases

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(d) Dehydrating Agents
Very Short:

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1. Do boron halides form additional compounds with amines?

a
2. How does boron interact with NaOH? hs
at
3. What is the oxidation state of C in
(a) CO
lp

(b) HCN
ita

(c) H2CO3
ig

(d) CaC2
.d

4. What is the state of hybridization of C in

w

(a) CO32-
w

(b) CCl4
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(c) diamond
(d) Graphite?
5. Give two examples of electron-deficient compounds.
6. Arrange the following halides of boron in the increasing order of acidic character
7. What is dry ice? Why is it so-called?
8. Write balanced equations to show hydrolysis reactions of CO32- and HCO3–.
9. Why boron does not form B3+ ion?
10. Which oxide of carbon is an anhydride of carbonic acid?
Short Questions:
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 THE P-BLOCK ELEMENTS
11

1. Although boric acid B(OH)3 contains three hydroxyl groups, yet it behaves as a monobasic
acid. Explain.
2. SiCl4 forms [SiCl6]2- while CCl4 does not form [CCl6]2- Explain.
3. Why does not silicon form an analogue of graphite?
4. Why carbon forms covalent compounds whereas lead forms ionic compounds?
5. How is borax prepared from?
6. Mention three important uses of borax.
Long Questions:

)
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1. SiCl. forms [SiCl]2- while CClL does not form [CCl]2-. Explain

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2. Borazine is more reactive than benzene. Why?
3. (i) What are the different oxidation states exhibited by the group 14 elements? Discuss the

la
stability of their oxidation states.

a
(ii) What type of oxides are formed by group 14 elements? Which of them are acidic,
neutral or basic?
hs
at
4. (a) [SiF6]2- is known whereas [SiCl6]2- is not known. Give reasons
lp

(b) Select the member (s) of group 14 that

(i) forms the most acidic oxide
ita

(ii) is commonly found in the +2-oxidation state

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(iii) used as a semi-conductor.

.d

(c) Explain why a diamond that is covalent has a high melting point?
w

(d) Discuss the reaction of silica with

w

(i) NaOH
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(ii) HE
5. (a) Carbon exhibits catenation, whereas silicon does not. Explain.
(b) How does boron differ from aluminum.
(c) Write the similarities between boron and silicon.
Assertion Reason Questions:
1. In the following questions, a statement of Assertion (A) followed by a statement of Reason
(R) is given. Choose the correct option out of the choices given below each question.
Assertion (A): If Aluminium atoms replace a few silicon atoms in three
dimensional network of silicon dioxide, the overall structure acquires a negative charge.

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 THE P-BLOCK ELEMENTS
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Reason (R) : Aluminium is trivalent while silicon is tetravalent.

(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.
2. In the following questions, a statement of Assertion (A) followed by a statement of Reason
(R) is given. Choose the correct option out of the choices given below each question.
Assertion (A): Silicon’s are water repelling in nature.

)
Reason (R) : Silicon’s are organosilicon polymers, which have (–R2SiO–) as

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repeating unit.

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(i) A and R both are correct and R is the correct explanation of A.

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(ii) Both A and R are correct but R is not the correct explanation of A.

a
(iii) A and R both are not true.
(iv) A is not true but R is true.
hs
at
Case Study Based Question:
lp

1. The heavier members of 13 and 14 groups besides the group oxidation state also show
ita

another oxidation state which is two units less than the group oxidation state. Down the
group (↓), the stability of higher oxidation state decreases and that of lower oxidation state
ig

increases. This concept which is commonly called inert pair effect has been used to explain
many physical and chemical properties of the element of these groups.
.d

(1) Heavier members of groups 13 exhibit oxidation state

w

(a) +3 only
w

(b) +1 only
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(c) +1 and +3 both

(d) +1, +2, +3
(2) Which among the following is the strongest oxidising agent?
(a) SiO2
(b) GeO2
(c)SnO2
(d) PbO2
(3) Which among the following is the strongest reducing agent?

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 THE P-BLOCK ELEMENTS
11

(a) GaCl
(b) InCl
(c) BCl3
(d) TlCl
(4) The strongest reductant among the following is
(a) SnCl2
(b) SnCl4
(c) PbCl2

)
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(d) GeCl2

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(5) Which of the following statement is wrong?
(a) Tl(III) salt undergo disproportionation.

la
(b) CO is used as a reducing agent.

a
(c) CO2 is a greenhouse gas. hs
(d) SiO2 is a covalent solid.
at
Answer Key:
lp

MCQ
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1. (b) I, II and III

ig

2. (b) B > P > As > Bi

.d

3. (a) 6P-P single bonds are present

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4. (d) Polymorphic
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5. (c) Reaction between Zn and conc. H2SO4

(w

6. (c) Cristobalite
7. (a) Has carbon atoms arranged in large plates of rings of strongly bound carbon atoms with
weak interpolate bonds
8. (a) Alkaline solution
9. (c) C−Cl > C−Br > C−I
10.(a) Potassium Borate + Dihydrogen
11.(a) The oxygen-oxygen bond length in ozone is identical with that of molecular oxygen
12.(d) S2O2-7
13.(a) BF3

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 THE P-BLOCK ELEMENTS
11

14.(b) Urea
15.(b) Lewis Acids
Very Short Answer:
1. Boron halides are Lewis’s acids and hence accept a pair of electrons from amines to form
additional compounds.
2. 2B + 6NaOH → 2Na3BO3 + 3H2.
3. (a) + 2
(b) +2

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(c) +4

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(d) -1
4. (a) sp2

a la
(b) sp3 hs
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(c) sp3
lp
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(d) sp2
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5. BF3 and B2H6.

6. BF3 < BCl3 < BBr3 < BI3.
.d
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7. Solid CO2 is known as dry ice. It does not wet a piece of paper/cloth and sublimes without
melting. Therefore, it is called dry ice.
w

8. CO32- + H2O ⇌ OH– + HCO3–

(w

HCO3– + H2O ⇌ OH– + H2CO3.

9. Boron has a very high sum of the first three ionisation enthalpies. Hence it cannot lose three
electrons to form a B3+ ion.
10. CO2, because H2CO3 acid decomposes to give H2O and CO2.
Short Answer:
Ans: 1.

(26)
 THE P-BLOCK ELEMENTS
11

Hydrated species

)
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B(OH)3 is not a protonic acid.

.co
It behaves as a Lewis acid because it abstracts a pair of electrons from hydroxyl ion.
Ans: 2. Carbon does not have d-orbitals and hence C. Cl4 does not combine with Cl– ions to give

la
[CCl6]2-, On the other hand, silicon has vacant 3d-orbitals and thus can expand its covalency
from 4 to 6. Therefore, SiCl4 combines with CL ions to form [SiCl6]2-

a
hs
at
SiCl4 + 2Cl– → [SiCl6]2-
lp

Ans: 3. In graphite, C is sp2 hybridised and each C is linked to three other C atoms forming
ita

hexagonal rings. Thus, graphite has a two-dimensional sheet-like structure.

ig
.d

Silicon, on the other hand, does not form an analogue of C because of the following two
reasons:
w
w

1. Silicon has a much lesser tendency for catenation than C as Si-Si bonds are much weaker
(w

than C-C bonds.

2. Silicon because of its larger size than C undergoes sp3 hybridisation.
Ans: 4. Carbon cannot lose electrons to form C4 because the sum of four ionisation enthalpies
is very high. It cannot gain four electrons to form C4 because energetically it is not favorable.
Hence C forms only covalent compounds. Down the group 14, ionisation enthalpies decrease,
Pb being the last element has so low I.E. that it can lose electrons to form ionic compounds.
Ans: 5. (I) Borax is also called sodium tetraborate decahydrate (Na2B4O7.10H2O). It can be
prepared as follows:
From colemanite: Powdered mineral is boiled with sodium carbonate solution and filtered. The
filtrate is concentrated and then cooled when crystals of borax.

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 THE P-BLOCK ELEMENTS
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Ca2B6O11 + 2Na2CO3 → Na2B4O7 + 2NaBO2 + 2CaCO3.

The mother-liquor which contains sodium meta-borate is treated with a current of C02, to
convert it into borax which separates out.
4NaBO2 + CO2 → Na2B4O7 + Na2CO3
(ii) From Tincal: Tincal obtained from dried up lakes is boiled with water. The solution is filtered
to get rid of insoluble impurities of clay, sand etc. The filtrate is concentrated to get the crystals
of borax.
(iii) From boric acid: Boric acid is neutralised with sodium carbonate and the resulting solution
is concentrated and cooled to get the crystals of borax Na2B4O7.10H2O.

)
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4H3BO3 + Na2CO3 → Na2B4O7 + 6H2O + CO2 ↑

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Ans: 6. It is used:
• As a flux soldering and welding in industry.

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• In the manufacture of borosilicate glass (or pyrex glass).

a
• In making enamels and glazes. hs
• In stiffening of candle wicks.
at
• In softening of water.
lp

• In a qualitative analysis for borax bead test in the laboratory.

ita

Long Answer:
ig

Ans: 1. Carbon does not have d-orbitals, hence CCl4 does not combine with Cl ions to form [CCl6]2-
.d

. On the other hand, silicon has vacant 3-d orbitals & thus SiCl4 combines with Cl– ions to form
w

[Sicy2-
w

SiCl4 + 2Cl– → [SiCl6]2-

(w

In other words, carbon shows a fixed covalency of 4 but silicon exhibits varying covalency from 4
to 6.
Ans: 2. Both Borazine & Benzene are isoelectronic. In benzene C = C bonds are non-polar while
N=B bonds in borazine are polar in nature due to the presence of a co-ordinate bond between N
& B atoms. As a result, addiction is quite frequent in borazine while it is less in benzene because
of delocalization of π-electron charge.

Ans: 3. (i) The group 14 elements have four electrons in the outermost shell. The common
oxidation states exhibited by these elements are +4 and +2. Since the sum of the first four
ionisation enthalpies is very high, compounds in the +4-oxidation state are generally covalent in
nature. In heavier members such as Ge, Sn and Pb, the tendency to show +2 oxidation state

(28)
 THE P-BLOCK ELEMENTS
11

increases. It is due to the inability of ns2 electrons of the valence shell to participate in bonding.

The relative stabilities of these two oxidation states vary down the group. C and Si mostly show a
+4 oxidation state. Ge forms stable compounds in the +4 state and only a few compounds in the
+2 state. Sn forms compounds in both oxidation states (Sn in +2 state is a reducing agent).

Lead compounds in the +2 state are stable and in the +4 state are strong oxidising agents. In the
tetravalent state, the number of electrons around the central atom in a molecule (e.g., carbon in
CCl4) is eight. Being electron precise molecules, they are normally not expected to act as an

)
electron acceptor or electron donor.

m
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Although carbon cannot exceed its covalence of more than 4, other elements of the group can do

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so. It is because of the presence of d-orbital in them. Due to this, their halides undergo hydrolysis
and have a tendency to form complexes by accepting electron pairs from donor species. For

a
example, the species like SiF5–, SiF6–, [GeCl6]2-, [Sn(OH)6]2- exist where the hybridisation of the
hs
central atom is sp3d2.
at
lp

(ii) All members when heated in oxygen form oxides. There are -mainly two types of oxides, i. e.,
monoxide and dioxide of formula MO and MO2 respectively. SiO only exists at high temperature.
ita

Oxides in the higher oxidation state of elements are generally more acidic than those in the lower
oxidation state. The dioxides-CO2, SiO2 and GeO2 are acidic, whereas SnO2 and PbO2 are
ig

amphoteric in nature. Among monoxides, CO is neutral, GeO is distinctly acidic whereas SnO and
.d

PbO are amphoteric.

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Ans: 4. (a) (i) [SiF6]2- is known whereas [SiCl6]2- does not exist.
w

The main reasons are (i) six large chlorine atoms cannot be accommodated around silicon atom
(w

due to the limitation of their size.

(ii) Interactions between lone pairs of a chlorine atom and silicon atom are not very strong
(b) (i) The most acidic dioxide is formed by carbon (CO2).
(ii) Lead is mostly found in the +2 oxidation state in its compounds.
(iii) Silicon and germanium are used as semiconductors.
(c) Though diamond has covalent bonding in it, yet it has a high melting point, because a diamond
has a 3-dimensional network involving strong C—C bond, which are very difficult to break and
in turn, it has a high melting point.
(d) (i) SiO2 reacts with HF as follows:

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 THE P-BLOCK ELEMENTS
11

SiO2 + 2NaOH → Na2SiO3 + H2O

(ii) SiO2 reacts with HF as follows:
SiO2 + 4HF → SiF4 + 2H2O.
Ans: 5. (a) Carbon shows catenation because of its smaller size, high bond energy of C – C bond,
the possibility of sp, sp2, sp3 hybridisation and formation of multiple bonds C-C (1σ), C = C (1σ +
S1π),- C = C (1σ + 2π). On the other hand, silicon shows only limited catenation because of its
large atomic radius, low bond energy of Si-Si bond and absence of multiple bonds between Si
atoms.
(b) Difference between boron and aluminum:

)
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1. Boron is a non-metal but aluminum is a metal.

.co
2. Boron is a semi-conductor while aluminum is a good conductor of electricity.
3. Boron forms a number of hydrides called boranes, but Al forms a polymeric hydride.

la
4. Halides of boron (except BF3) are readily hydrolysed by water whereas halides of A1 are

a
only partially hydrolysed by water.
5. B2O3 is acidic, but Al2O3 is amphoteric.
hs
at
6. Boron hydroxide B(OH)3 is acidic, but Al(OH)3 is amphoteric.
lp

(c) Similarities between boron and silicon:

ita

1. Both are non-metals.

2. Both are semi-conductors
ig

3. Boron and silicon form a number of covalent hydrides which have similar properties. For
.d

example, they spontaneously catch fire on exposure to air and are readily hydrolysed by
w

water.
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4. The halides of boron and silicon are readily hydrolysed by water.

(w

5. Boron trioxide (B2O3) and silicon dioxide (SiO2) are acidic in nature. These dissolve in
alkali solution forming borates and silicates.
Assertion Reason Answer:
1. (i) Both A and R are correct and R is the correct explanation of A.
2. (ii) Both A and R are correct but R is not the correct explanation of A.
Case Study Answer:
1. Answer:
(1) (c) +1 and +3 both
(2) (d) PbO2

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 THE P-BLOCK ELEMENTS
11

(3) (c) BCl3

(4) (d) GeCl2
(5) (a) Tl(III) salt undergo disproportionation.

)
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a la
hs
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(31)
 CHEMISTRY

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CHAPTER 12: ORGANIC CHEMISTRY SOME BASICPRINCIPLES AND

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TECHNIQUES

a
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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

ORGANIC CHEMISTRY SOME BASICPRINCIPLES AND

TECHNIQUES

Introduction

In this chapter, we shall discuss some basic principles and techniques of analysis needed for
understanding the formation and properties of organic compounds. Organic compounds are
essential for existence and maintenance of life on earth. These include complex molecules like

)
(DNA) which carry genetic information and proteins which is building blocks of life. Organic

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compounds also play an important role in material used in daily life such as cloths, fuel, dyes,

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and medicines etc.

la
Structural Representations of Organic Compounds

a
hs
Structural Formulas
at
The Lewis structures can be simplified by representing the two electron covalent bonds by a
lp

dash (–). In this representation, a single bond is represented by a single dash (–), a double bond
ita

by a double dash (=) and a triple bond by a triple dash (≡). The lone pair on an atom may or may
not be shown. This representation is called structural formula.
ig
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Condensed Formulas

In this formula, the arrangement of atoms are shown but the bonds between may be omitted
and the number of identical groups attached to an atom are indicated by a subscript.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

Condensed Formulas

)
In this representation, the carbon and hydrogen atoms are not shown and the lines between

m
carbon-carbon bonds are shown in a zig-zag manner.

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a la
hs
at
lp
ita
ig
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w
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In cyclic compounds, the bond-line formulas may be given as follows:

(w

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

Three-dimensional representation of organic molecules

The three-dimensional (3-D) structure of organic molecules can be represented on paper by

using certain conventions. In these formulae, the thick solid (or heavy) line or the solid wedge
indicates a bond lying above the plane of the paper and projecting towards the observer while
a dashed wedge is used to represent a bond lying below the plane of the paper and projecting
away from the observer.

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a la
hs
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Classification of Organic Compounds
lp
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On the basis of their structures, organic compounds are broadly classified as follows:
ig
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Open Chain Compounds

These compounds contain open chains of carbon atoms in their molecules. The carbon chains
may be either straight chains or branched chains. They are also called aliphatic compounds.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

Closed Chain or Ring Compounds

)
These compounds contain chains or rings of atoms in their molecules.

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Alicyclic Compounds: These compounds contain a ring of three or more carbon atoms in them.

.co
They resemble aliphatic compounds in many of their properties.

a la
hs
at
Aromatic Compounds: These have a cyclic system containing at last one benzene ring. The
parent member of the family is called benzene. Benzene has a homocyclic hexagonal ring of six
lp

carbon atoms with three double bonds in the alternate positions.

ita
ig
.d
w
w
(w

Heterocyclic Compounds: In these compounds, the ring contains one or more atoms of either
nitrogen, oxygen or sulphur in addition to carbon atoms. The atom other than carbon (such as
N, O, S) present in the ring is called hetero atoms.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

Functional Groups: An atom or group of atoms which largely determines the properties of the
organic compounds particularly the chemical properties.

)
m
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a la
Homologous Series: Homologous series may be defined as “a series of similarly constituted
hs
compounds in which the members possess the same functional group and have similar
chemical characteristics”. The two consecutive members differ in their molecular formula by –
at
CH2– group.
lp

1. CH3OH - Methyl alcohol

ita

2. C2H5OH - Ethyl alcohol

3. C3H7OH - Propyl alcohol
ig

4. C4H9OH - Butyl alcohol

.d

5. C5H11OH - Pentyl alcohol

w

6. C6H13OH - Hexyl alcohol

w
(w

Nomenclature of Organic Compounds

The term ‘nomenclature’ means the system of naming of organic compounds. There are two
systems of nomenclature:

1. Trivial or Common System

In this nomenclature, the names of organic compounds were assigned based on their source
of origin or certain properties. For instance, citric acid got its name from the source (citrus
fruits) from which it was first isolated. Formic acid was named so as it was first obtained from
red ant. In Latin ant word is formica.

2. IUPAC System of Nomenclature

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

A systematic method of naming has been developed and is known as the IUPAC (International
Union of Pure and Applied 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.

Free Radicals
Free Radical
A free radical may be defined as an atom or a group having an odd or unpaired

)
electron.These are generally produced by homolytic cleavage of a covalent bond.

m
.co
a la
hs
at
lp
ita
ig
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Classification of Free Radicals

w

Free radicals are also classified as primary (1°), secondary (2°) and tertiary (3°)
w

according as the carbon carrying the unpaired electron is primary, secondary and
(w

tertiary.

Stability of Free Radicals

The order of stability of free radicals is the same as that of carbocations i.e. 3° >2° >1°

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

This order of stability can be explained on the basis of hyperconjugation.

Greater the number of alkyl groups attached to the carbon atom carrying the odd
electrons, greater is the delocalization of the odd electrons and hence more stable is
the alkyl free radical.

)
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a la
Stability of free radical hs
at
Allyl and benzyl free radicals are stabilized by resonance.
lp
ita
ig
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w
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Greater the number of phenyl groups more stable is the free radical.

Free radicals are also very short-lived highly reactive chemical species because of the
strong tendency of the carbon atom carrying the odd electron to acquire one more
electron to complete its octet.
Orbital structure of Free Radicals

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

)
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Alkyl free radicals are planar chemical species.In free radicals, the unhybridized p-

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orbital contains the odd electron.

la
Like carbanions , free radicals can also assume pyramidal shape since the energy
difference between planar and pyramidal shape is not much.

a
Stereoisomerism
hs
at
Isomers which have same structural formula but have different relative arrangement or
lp

atoms or groups in space are called stereoisomers and the phenomenon is called
stereoisomerism.
ita

cis-trans isomerism is an example of stereoisomerism.

ig

cis-trans isomers
.d

Due to π-bonding between the two carbon atoms, the rotation around carbon-carbon
w

double bond is prohibited and hence the geometry of the atoms or groups attached to
w

the carbon atoms gets fixed in space.

(w

Stereoisomerism is also called geometrical isomerism.

Steric Hindrance

If two non-bonded atoms or groups in an organic molecule are held together at a

distance equal to or less than the sum of their van der waal radii, then they repel each
other due to spatial crowding.This repulsion is referred to as steric hindrance or steric
strain or van der waal strains.
Molecules which possess steric strain are relatively less stable as compared to those
having no steric strain.

For Example: Cis-but-2-ene has steric hindrance and hence is less stable as compared

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

to trans-but-2-ene which has no steric hindrance.

As the size of the atoms around a bulky atom increases, the steric hindrance increases
accordingly.

Summary-
1. Condensed Structural Formula: The structural formulae obtained by omitting some or all
the covalent bonds and by indicating the number of identical groups attached to an atom
by subscript is called condensed structural formula.

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2. Bond-line Structural Formula: In this formula of organic compounds, carbon and hydrogen

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atoms are not shown and line representing C –C bonds and drawn in zig-zag fashion. The
only atoms specifically written are those that are neither nor hydrogen bonded to carbon.

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3. Cyclic Compounds: These are compounds in which carbon atoms are joined in rings i.e.,

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they are closed chain compounds.

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4. Aromatic Compounds: Benzene and its derivatives are called aromatic compounds.
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5. Functional group: Functional group is an atom or group of atoms or reactive part of the
compound which determines physical and chemical properties of compounds.
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6. Homologous Series: Homologous series is a series of compounds which has same
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functional group same general formula and show gradation in physical and chemical
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properties of compounds.
7. Isomerism: The phenomenon of existence of two or more compounds possessing the same
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formula but different structural formula and different physical and chemical properties are
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called isomerism.
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8. Structural Isomerism: Compounds having the same molecular formula but different
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structures are classified as structural isomers. Chain Isomerism: The isomers, which differ
in carbon atom chain, are called chain isomers and this phenomenon is called chain
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isomerisms.
9. Position Isomerism: The isomers, which differ in position of substituent or functional
groups are called position isomers and this phenomenon is called position isomerism.
10.Functional Isomerism: Those isomers, which differ in functional groups are called
functional isomers and this phenomenon is called functional isomerism.
11.Metamerism: Those isomers, which differ in alkyl group attached with the di or tri valent
atom of functional group. These are called metamers and this phenomenon is called
metamerism.
12.Stereoisomerism: Those compounds that have the same composition and sequence of
covalent bond but differ in relative positions of their atoms or groups in space.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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13.Free Radical: An atom or group of atoms containing odd unpaired electrons in excited
state is known as free radical.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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Important Questions

Multiple Choice questions-

Question 1. Which among the following statement is not true?
(a) In liquid, particles are less regularly arranged and are free to move
(b) Boiling involves breaking up of group of molecules in liquid
(c) Boiling involves separation of oppositely charged ions

)
(d) Thermal energy of particles overcome cohesive forces that hold them

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Question 2. Identify the chiral molecule among the following:

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(a) Isopropyl alcohol

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(b) 2-pentanol

a
(c) 1-bromo 3-butene
(d) Isobutyl alcohol
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Question 3. Which element is estimated by Carius method?
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(a) Carbon
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(b) Hydrogen
(c) Halogen
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(d) Nitrogen
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Question 4. A solution of (+) – 2 – chloro – 2 – phenylethane in toluene racemises slowly in the

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presence of small amounts of SbCl5 due to the formation of

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(a) Carbanion
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(b) Carbene
(c) Free radical
(d) Carbocation
Question 5. Which of the following acids has the smallest dissociation constant?
(a) CH3CHFCOOH
(b) FCH2CH2COOH
(c) BrCH2CH2COOH
(d) CH3CHBrCOOH
Question 6. What is the correct IUPAC name of?

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

(a) 4-methoxy-2-nitrobenzaldehyde
(b) 4-formyl-3-nitro anisole
(c) 4-methoxy-6-nitrobenzaldehyde
(d) 2-formyl-5-methoxy nitrobenzene

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Question 7. 0.5 g of hydrocarbon gave 0.9 g water on combustion. The percentage of carbon in
hydrocarbon is

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(a) 75.8

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(b) 80.0

a
(c) 56.6 hs
(d) 28.6
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Question 8. 0.92 g of an organic compound was analysed by combustion method. The mass of
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the U- tube increased by 1.08 g. What is the percentage of hydrogen in the compound?
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(a) 13.04%
(b) 52.17%
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(c) 65.21%
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(d) 11.30%
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Question 9. What is the state of hybridisation of carbon in carbanion?

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(a) sp
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(b) sp²
(c) sp³
(d) sp²d.
Question 10. An organic compound contains C = 38.8 H = 16 and N = 45.2. Empirical formula of
the compound is
(a) CH3NH2
(b) CH3CN
(c) C2H5CN
(d) CH2(NH)2

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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Question 11. 59 g of an amide obtained from a carboxylic acid, RCOOH, liberated 17 g of

ammonia upon heating with alkali. The acid is
(a) Formic Acid
(b) Acetic Acid
(c) Propionic Acid
(d) Benzoic Acid
Question 12. The displacement of electrons in a multiple bond in the presence of attacking
reagent is called

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(a) Inductive effect

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(b) Electrometric effect

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(c) Resonance

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(d) Hyper conjugation

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Question 13. The molecular formula C5H12 contains how many isomeric alkanes?
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(a) 1
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(b) 2
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(c) 3
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(d) 4
Question 14. If two compounds have the same empirical formula but different molecular
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formula, they must have

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(a) Different percentage composition

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(b) Different molecular weight

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(c) Same viscosity

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(d) Same vapour density

Question 15. Inductive effect involves
(a) Displacement of σ electrons
(b) Delocalization of π electrons
(c) delocalization of σ-electrons
(d) Displacement of π-electrons

Very Short:
1. What type, of hybridisation, is involved in

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

(i) planar and

(ii) linear molecules?
2. Arrange the following in increasing order of C – C bond strength:
C2H6, C2H4C2H2
3. Arrange the following in decreasing order of C — C bond length:
4. What is the type of hybridisation of C atoms in benzene?
5. What are isomers?

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6. Select electrophiles out of the following:

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H+ Na+, Cl–, C2HSOH, AlCl3, SO3, CN–, CH3CH2+,: CCl2, R-X.

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7. Select nucleophiles from the following.
BF3 NH3 OH–, R-X, C2H5OH, H3O+, NO2, CN–.

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8. Give the I.U.P.A.C. names of the following compounds

a
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(v) (CH3)4C
(vi) (CH3)2CHCOOH.
9. What is a functional group?
10. Arrange the following in increasing order of-I effect.
(i) -NO2, -COOH, -F, -CN, – I.

Short Questions:
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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

1. Expand each of the following bond-line formulae to show all the atoms including carbon
and hydrogen.

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(d)
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2. For each of the following compounds, write a more condensed and also their bond line
formulae.
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3. What is the type of hybridisation of each carbon in the following compounds?

(a) CH3Cl
(b) (CH3)2CO
(c) CH3CN

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

(d) HCONH2
(e) CH3CH = CHCN.
4. What is the shape of the following molecules:
(a) H2C = O
(b) CH3F
(c) H-C ≡ N?
5. Give the I.U.P. A.C. names of the following compounds:

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(ii) CH3 – CH = CH COOH

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(iii) (CH3)2C = CHCOCH3

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(vi) CH2 = CH – CN.

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6. Write the I.U.P.A.C. names of

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Long Questions:
1. Explain the principle of steam distillation.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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2. Dehydrobromination of compounds (A) and (B) yield the same alkene (c) Alkene (c) Can
regenerate (A) and (B) by the addition of HBr in the presence and absence of peroxide
respectively. Hydrolysis of A and B give isomeric products (D) and (E) respectively. 1, 1-
Diphenyl ethane is obtained on the reaction of (C) of benzene in the presence of H+ ions.
Give structures of A to E with reactions.
3. What are reaction intermediates? How are they generated by bond fission?
4. 0.395 g of an organic compound by various method for the estimation of sulphur gave
0.582g of BaS04. Calculate the percentage of Sulphur.
5. 0.15g of an organic compound gave 0.12g of AgBr by carius method. Find the percentage of

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bromine in the compound.

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Assertion Reason Questions:

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1. In the following questions, a statement of Assertion (A) followed by a statement of Reason
(R) is given. Choose the correct option out of the choices given below each question.

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Assertion (A) : Simple distillation can help in separating a mixture of
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propan-1-ol (boiling point 97°C) and propanone (boiling point 56°C).
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Reason (R) : Liquids with a difference of more than 20°C in their boiling
points can be separated by simple distillation.
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(i) Both A and R are correct and R is the correct explanation of A.

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(ii) Both A and R are correct but R is not the correct explanation of A.
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(iii) Both A and R are not correct.

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(iv) A is not correct but R is correct.

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2. In the following questions, a statement of Assertion (A) followed by a statement of Reason

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(R) is given. Choose the correct option out of the choices given below each question.

Assertion (A) : Energy of resonance hybrid is equal to the average of energies

of all canonical forms.
Reason (R) : Resonance hybrid cannot be presented by a single structure.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

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Case Study Based Question:

1. Read the passage given below and answer the following questions:
The electron displacements due to the influence of an atom or a substituent group
present in the molecule cause permanent polarisation of the bond (called electronic effect),
e.g.

In above example, polar C—F bond induce polarity in the adjacent bonds. Such polarisation

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of adjacent σ- bond is referred to as the inductive effect. This effect decreases rapidly as the

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number of intervening bonds increases. The resonance effect is defined as the polarity

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produced in the molecule by the interaction of two π-bonds or in conjugated system.
When the group or atom release electron density then electron density of conjugated

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system increases while the group or atom attract/withdraw electron density then electron

a
density of conjugated system decreases.
hs
(1) In which molecule dipole moment is the maximum?
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(2) In which benzene ring electron density is maximum?

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(3) Which of the following system show abnormal behaviour in their properties (like-
stability, polarity ... etc.) ?

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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(4) The permanent displacement of electron through a chain involving only σ-bonds is called

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(a) Inductive effect

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(b) Hyperconjugation effect

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(c) Electrometric effect

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(d) Mesmeric effect

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2. Read the following passage and answer the question accordingly.
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An intermediate is a molecular entity, that is formed from the reactants and reacts further
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to give the directly observed products of a chemical reaction. Most chemical reactions are
stepwise, that is they take more than one elementary step to complete. An intermediate is
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the reaction product of each of these steps, except for the last one, which forms the final
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very isolated. Also, owing to the short lifetime, they do not remain in the product mixture.
In certain cases, they are separated and stored. For example matrix isolation and low
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temperature. Matrix isolation is a technique that is used experimentally in physics and

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chemistry that includes a material that has been trapped with in an unreactive material.
Host matrix generally comprises guest particles that are generally embedded. Guest
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particles can be molecules, atoms and ions. The guest is isolated within the host matrix.
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(1) Relative stabilities of the following carbocations will be in the order

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(a) C > B > A

(b) C < B < A
(c) B > C > A
(d) C > A > B
(2) CH3 CH2 Cl undergoes homolytic fission, produces.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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(3) The shape of carbocation is:

(a) square planar
(b) trigonal planar
(c) octahedral
(d) trigonal pyramidal

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(4) Compare stability of free radicals.

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(a) II > I > III > IV

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(b) II > I > IV > III

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(c) I > II > III > IV

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(d) IV > III > I > II

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Answer Key:
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MCQ
1. (c) Boiling involves separation of oppositely charged ions

2. (d) Isobutyl alcohol

3. (c) Halogen

4. (d) Carbocation

5. (c) BrCH2CH2COOH

6. (a) 4-methoxy-2-nitrobenzaldehyde

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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7. (b) 80.0

8. (a) 13.04%

9. (c) sp³

10.(a) CH3NH2

11.(b) Acetic Acid

12.(b) Electrometric effect

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13.(c) 3

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14.(b) Different molecular weight

15.(a) Displacement of σ electrons

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Very Short Answer: hs
1. (i) sp2
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(ii) sp.
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2. C2H6 < C2H4 < C2H2.

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3. C2H6 > C2H4 > C2H2.

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4. It is an sp2 type of hybridisation.

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5. Compounds having the same molecular formula, but different physical and chemical
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properties are called isomers.

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6. H+, Na+, A1Cl3, SO3, CH3CH2+,: CCl2, R-X.

7. NH3, OH, C2H5OH, CN

8. (i) 2-Bromo-4 – methyl pent-3- one
(ii) 4-Methyl-2-nitro pent – 3 – one
(iii) 2 – Ethoxy – 4 – methoxypent – 3 – one
(iv) 2-Bromo-4-nitro pent-3-one
(v) 2, 2-Dimethylpropane

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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(vi) 2-Methyl propanoic acid.

9. The atom or group of atoms present in a molecule that determines its chemical properties is
called the functional group.
10. -I < -F < -COOH < -CN <NO2.

Short Answer:
Ans: 1.

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(a)

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(b)
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(c)

(d)

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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Ans: 2. (a) Condensed formulae are

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(CH3)2CH CH2 OH

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(b) CH3(CH2)5 CHBr CH2 CHO

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(c) HO(CH2)3 CH(CH3) CH(CH3)2

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(d) HOCH(CN)2
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Ans: 3.

(a)

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

(b)

(c)

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(d)

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(d)
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Ans: 4. (a) In H2C = O; C is sp2 hybridised, hence its shape is H trigonal planar
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(b) In CH3F -F; C is sp3 hybridized

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∴ it is tetrahedral

(c) In H-C ≡ N; C is sp-hybridized, hence HCN is linear

H—C ≡ N.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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Ans: 5. (i) 2-Ethylprop-2-en-l-ol

(ii) But-2-en-l-oic acid

(iii) 4-Methylpent-3-en-2-one

(iv) 3-Chloropropanal

(v) 3-Methylbutane-l-al

(vi) Prop-2-en-1-nitrile.

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Ans: 6. (i) 3-Ethyl-4-methylhept-5-en-2-one

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(ii) 2-Ethyl-3-methylpent-2-en-1 -one.

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Long Answer:

a
hs
Ans: 1. Steam distillation: The process of steam distillation is employed in the purification of
substance from non-volatile impurities provided the substance itself is volatile in steam and
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insoluble in water.
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This method is based on the facts that

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1. A liquid boils at a temperature when its vapour pressure becomes equal to the
atmospheric pressure.
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2. The vapour pressure of a mixture of two immiscible liquids is equal to the sum of the
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vapour pressures of the individual liquids.

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In the actual process, steam is continuously passed through the impure organic liquid. Steam
heats the liquid and it gets practically condensed to water. After some time, mixture of the liquid
and water begins to boil, because the vapour pressure of the mixture becomes equal to the
atmospheric pressure.

Obviously, this happens at a temperature that is lower than the boiling point of the substance or
that of water. Thus an organic compound boils below its boiling points and chances of
decomposition avoided. For example, a mixture of aniline (b.p 453 K) with decomposition and
water (b.p. 373 K) under normal atmospheric pressure boils at 371K. At this temperature the

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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Steam Distillation

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water boils at 371 K. At this temperature, the vapour pressure of water is 717 mm and that of

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aniline is 43 mm and therefore the total pressure is equal, to 760 mm. Thus in steam
hs
distillation, the liquid gets distilled at a temperature lower than its boiling point and chances of
decomposition avoided. The proportion of water and liquid in the mixture that distils over is
at
given by the relation.
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where w1 and w2 stand for the masses of water and liquid that distils over. P1 and P2 are vapour
pressure of water and of liquid at the distillation temperature and M is the molecular mass of
w

the liquid.
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Ans: 2. Alkene (C) on reaction with benzene in the presence of H+ ions give 1, 1-Diphenyl ethane.
Therefore, C must be styrene as depicted below

Now dehydrobromination of A and B give the same alkene C, i.e.,

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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styrene.
∴ A and B must be isomeric alkyl bromide

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A and B can be obtained by the addition of HBr in the presence and absence of peroxide to

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styrene.

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Hydrolysis of A and B give isomeric alcohols (D) & (E) as

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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Ans: 3. The species which are generated as a result of bond fission are called reaction

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intermediates. The important reaction intermediates are:
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1. Free Radicals: A free radical may be defined as an atom or group of atoms having an impaired
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electron. These are obtained as a result of homolytic fission of covalent bonds.
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These free radicals are neutral particles, extremely transient, (short-lived) and highly reactive.
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They get consumed as soon as they are formed. They pair up their electron with another
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electron from wherever it is available. They occur only as a reaction intermediate. Their
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presence is felt in reactions, but cannot be isolated in a free state. For example dissociation of
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Cl2 gas in the presence of Ultraviolet light produces free radicals.

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The alkyl free radicals are obtained when free radical: Cl reacts with alkanes.

Free radical may be primary, secondary, tertiary depending upon whether, one, two or three
carbon atom attached to the carbon atoms carrying the odd electron.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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The stability is CH3 < 1° < 2° < 3°.

2. Carbocation or carbonium ion: It is defined as a group of atoms that contain positively charged

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carbon having only six electrons. It is obtained by heterolytic fission of a covalent bond
involving a carbon atom.

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They are also classified as primary, secondary and tertiary depending upon whether one, two
or three carbon atoms are attached to the carbon bearing the positive charge as:
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Thus, the order of stability if CH3+ < 1° < 2° < 3°.

3. Carbanion: A carbanion may be defined as a species containing a carbon atom carrying a

negative charge. These are generated by the atom in which the atom linked to carbon goes
without the bonding electrons. As a result of this carbon acquires a negative charge. For
example, the removal of hydrogen of methyl part of acetaldehyde molecule as H+ ion leaving
both the electron on carbon.

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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They are also very reactive species. They are also classified as primary, secondary and tertiary
depending upon whether one, two or three carbon atoms are attached to the carbon atom
bearing negative
charge.

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The order of stability is the reverse of free radicals and carbocations
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CH3 – > 1° > 2° > 3°.

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(iv) Carbenes: The carbenes are reactive neutral species in which carbon atom has six
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electrons in the valency shell out of which two are shared. The simplest carbene is methylene
(CH2). It is formed when diazomethane is decomposed by the action of light.
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It is very reactive. It reacts with alkenes by adding to the double bond forming cyclopropane.

Ans: 4. Mass of BaSO4 = 0.582 g

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
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BaSO4 = S

233 = 32

233g of BaSO4 contain sulphur = 32g

0. 582 g of BaSO4 contains sulphur

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Ans: 5. Mass of AgBr formed = 0.12g
hs
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188 g of AgBr contains bromine = 80g.
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Therefore, 0.12g of AgBr will contain bromine

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80 × 0.12
= = 0.051 g
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188
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0.051
Percentage of bromine = × 100 = 34%
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0.15
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Assertion Reason Answer:

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1. (i) Both A and R are correct and R is the correct explanation of A.

2. (iv) A is not correct but R is correct.

Case Study Answer:

1. Answer:

(1) (b) CH3 CH2 CH2 — NO2

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 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES & TECHNIQUES
12

(2)

(3)

(4) (a) Inductive effect

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2. Answer:

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(1) (a) C > B > A

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(2) hs
(3) (b) trigonal planar
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(4) (b) II > I > IV > III

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(33)
CHEMISTRY

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CHAPTER 13: HYDROCARBONS

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 HYDROCARBONS
13

HYDROCARBONS

Introduction

The term ‘hydrocarbon’ is self-explanatory meaning compounds of carbon and

hydrogen only. Hydrocarbons hold economic potential in our daily life.
Natural gas and petroleum are chief sources of aliphatic hydrocarbons at the
present time, and coal is one of the major sources of aromatic hydrocarbons.

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Petroleum is a dark, viscous mixture of many organic compounds, most of
them being hydrocarbons, mainly alkanes, cycloalkanes and aromatic

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hydrocarbons.

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Classification

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As we are quite aware that there are different types of hydrocarbons. Depending
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upon the types of carbon-carbon bonds present, they can be classified into
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three main categories:

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1. Saturated hydrocarbons.
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2. Unsaturated hydrocarbons.
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3. Aromatic hydrocarbons.
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Saturated hydrocarbons contain carbon-carbon and carbon-hydrogen single bonds.

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If different carbon atoms are joined together to form open chain of carbon
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atoms with single bonds, they are termed as alkanes. On the other hand, if
carbon atoms form a closed chain or ring, they are termed as cycloalkanes.
Unsaturated hydrocarbons contain carbon-carbon multiple bonds – double
bonds, triple bonds or both. Aromatic hydrocarbons are a special type of
cyclic compounds.

Alkanes

These are the saturated chains of hydrocarbons containing carbon-carbon single

bonds. Methane (CH4) is the first member of this family containing single
carbon atom. Since it is found in coal mines and marshy areas, is also known

(1)
 HYDROCARBONS
13

as ‘marsh gas’. These hydrocarbons exhibited low reactivity or no reactivity

under normal conditions with acids, bases and other reagents, they were
earlier known as paraffins. The general formula for alkane is CnH2n + 2, where n
stands for number of hydrogen atoms in the molecule.

)
m
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a la
hs
at
Structure of Methane
lp

1. Nomenclature
ita

For nomenclature of alkanes in IUPAC system, the longest chain of carbon atoms
containing the single bond is selected. Numbering of the chain is done from
ig

the one end so that maximum carbon will be included in chain. The suffix
.d

‘ane’ is used for alkanes. The first member of the alkane series is CH 4 known
w

as methylene (common name) or methene (IUPAC name). IUPAC names of a

few members of alkenes are given below:
w
(w

S. No. Structure IUPAC Name

1. CH4 Methane
2. C2H6 Ethane
3. C3H8 Propane
4. C4H10 Butane
5. C5H12 Pentane
6. C6H14 Hexane
7. C7H16 Heptane
8. C8H18 Octane

(2)
 HYDROCARBONS
13

9. C9H20 Nonane
10. C10H22 Decane

2. Preparation of Alkanes
Though petroleum and natural gas are the main sources of alkanes, it can be
prepared by several other methods as well.

i. From unsaturated hydrocarbons: The addition of dihydrogen to unsaturated

)
hydrocarbons like alkenes and alkynes in the presence of a suitable catalyst

m
under a given set of conditions produces saturated hydrocarbons or alkanes.

.co
This process of addition of dihydrogen is known as hydrogenation process.
CH2＝CH2 + H2 ⟶ CH3-CH3

la
CH☰CH + 2H2 ⟶ CH3-CH3

a
ii. From alkyl halides hs
a) Reduction: Alkyl halides undergo reduction with zinc and dilute hydrochloric
at
acid to give alkanes. In general, the reaction can be represented as
lp

CH3-Cl ⟶ CH4
ita

b) Wurtz reaction: Alkyl halides on treatment with sodium metal in dry ether
give higher alkanes. This reaction is known as Wurtz reaction.
ig

CH3Br + 2Na + BrCH3 ⟶ CH3-CH3 + 2NaBr

.d

iii. From carboxylic acids

w

a) By decarboxylation of carboxylic acids: Sodium salts of carboxylic acids on

w

heating with soda lime give alkanes containing one carbon atom less than the
(w

carboxylic acid. A molecule of carbon dioxide is eliminated which dissolves in

NaOH to form sodium carbonate.
CH3COONa + NaOH ⟶ CH4 + Na2CO3
b) Kolbe’s electrolytic method: An aqueous solution of sodium or potassium salt
of a carboxylic acid on electrolysis gives alkane containing even number of
carbon atoms at anode.
CH3COONa + 2H2O ⟶ CH3-CH3 + 2CO2 + H2 + NaOH
3. Properties of Alkanes
I. Physical Properties
i. State: Due to the weak van der Waals forces, the first four members C1 to C4

(3)
 HYDROCARBONS
13

i.e., methane, ethane, propane and butane are gases. From C5 to C17 are
liquids and those containing 18 carbon atoms or more are solids at 298 K.
They all are colourless and odourless.
ii. Solubility: Alkanes are generally insoluble in water or in polar solvents, but
they are soluble in non-polar solvents like, ether, benzene,
carbontetrachloride etc. The solubility of alkanes follow the property “Like
Dissolves like”.
iii. Boiling point: The boiling points of straight chain alkanes increase regularly
with the increase of number of carbon atoms. This is due to the fact that the

)
intermolecular van der Waals forces increase with increase in the molecular

m
size or the surface area of the molecule.

.co
II. Chemical Properties

la
Generally, alkanes show inertness or low reactivity towards acids, bases, oxidizing
and reducing agents at ordinary conditions because of their non-polar nature

a
and absence of π bond. The C–C and C–H bonds are strong sigma bonds which
hs
do not break under ordinary conditions but they undergo certain reactions
at
under given suitable conditions.
lp

i. Halogenation reaction: When hydrogen atom of an alkane is replaced by a

halogen, it is known as halogenation reaction. Halogenation takes place either
ita

at high temperature (300–500°C) or in the presence of diffused sunlight or

ultraviolet light.
ig

CH4 + Cl2 ⟶ CH3Cl + HCl

.d

ii. Combustion: Alkanes on heating in presence of air gets completely oxidized

w

to carbon dioxide and water. It burns with a non-luminous flame. The

w

combustion of alkanes is an exothermic process i.e., it produces a large

amount of heat.
(w

CH4 + 2O2 ⟶ CO2 + 2H2O

iii. Controlled oxidation: When methane and dioxygen compressed at 100 atm
are passed through heated copper tube at 523K yield methanol.
2CH4 + O2 ⟶ 2CH3OH
iv. Aromatization: The conversion of aliphatic compounds into aromatic
compounds is known as aromatisation. n-Alkanes having six or more carbon
atoms on heating to 773K at 10–20 atmospheric pressure in the presence of
oxides of vanadium, molybdenum or chromium supported over alumina get
dehydrogenated and cyclised to benzene and its homologues. This reaction is
also known as reforming.

(4)
 HYDROCARBONS
13

)
m
v. Reaction with steam: Methane reacts with steam at 1273K in the presence of

.co
nickel catalyst to form carbon monoxide and dihydrogen. This method is used
for industrial preparation of dihydrogen gas.

la
CH4 + H2O ⟶ CO + 3H2

a
Alkenes
hs
at
Alkenes are unsaturated hydrocarbons containing at least one carbon-carbon
lp

double bond with general formula CnH2n. Alkenes are also known as olefins
ita

(oil forming) since the first member, ethylene or ethene (C2H4) was found to
form an oily liquid on reaction with chlorine.
ig

1. Nomenclature
.d

For nomenclature of alkenes in IUPAC system, the longest chain of carbon atoms
w

containing the double bond is selected. Numbering of the chain is done from
w

the end which is nearer to the double bond. The suffix ‘ene’ replaces ‘ane’ of
alkanes. The first member of the alkene series is C2H4 known as ethylene
(w

(common name) or ethene (IUPAC name). IUPAC names of a few members of

alkenes are given below:

S.No. Structure IUPAC Name

1. C2H4 Ethene

2. C3H6 Propene

(5)
 HYDROCARBONS
13

3. C4H8 Butene

4. C5H10 Pentene

5. C6H12 Hexene

6. C7H14 Heptene

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7. C8H16 Octene

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8. C9H18 Nonene

a la
9. C10H20 Dekene
hs
at
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2. Preparation
ita

i. From alkynes: Alkynes undergo partial reduction with calculated amount of

ig

dihydrogen producing alkenes.

.d

CH☰CH + H2 ⟶ CH2＝CH2
w

ii. From alkyl halides: Alkyl halides (R–X) on heating with alcoholic potash
w

eliminates one molecule of halogen acid to form alkenes. This reaction is

(w

known as dehydrohalogenation i.e., removal of halogen acid.

CH3CH2Cl ⟶ CH2＝CH2 + HCl

iii. From alcohols by acidic dehydration: Alcohols on heating with concentrated

sulphuric acid form alkenes with the elimination of one water molecule since
a water molecule is eliminated from the alcohol molecule in the presence of
an acid, this reaction is known as acidic dehydration of alcohols.

CH3CH2OH ⟶ CH2＝CH2 + H2O

3. Properties of Alkenes

(6)
 HYDROCARBONS
13

I. Physical properties

i. The first three members of alkenes are gases, the next fourteen are liquids
and the higher ones are solids.

ii. Ethene is a colourless gas with a faint sweet smell. All other alkenes are
colourless and odourless, insoluble in water but fairly soluble in non-polar
solvents like benzene, petroleum ether.

iii. They show a regular increase in boiling point with increase in size i.e., every —

)
CH2 group added increase the boiling point by 20–30K.

m
II. Chemical properties

.co
i. Addition of dihydrogen: Alkenes adds one mole of dihydrogen gas in

la
presence of catalysts such as Ni at 200–250°C, or finely divided Pt or Pd at
room temperature to give an alkane.

a
CH2＝CH2 + H-H ⟶ CH3-CH3
hs
at
ii. Addition of halogens: Halogens like bromine or chlorine add up to alkene to
lp

form vicinal dihalides in presence of CCl4 as solvent. The order of reactivity of

halogens is F > Cl > Br > I.
ita

CH2＝CH2 + Br-Br ⟶ Br-CH2-CH2-Br

ig
.d

iii. Addition of hydrogen halides: Hydrogen halides (HCl, HBr, HI) add upto
alkenes to form alkyl halides. The order of reactivity of hydrogen halides is HI
w

> HBr > HCl. Like addition of halogens to alkenes, addition of hydrogen halides
w

is an example of electrophilic addition reaction.

(w

CH2＝CH2 + H-Br ⟶ CH3-CH2-Br

Markovnikov rule: According to the rule, the negative part of the addendum
(adding molecule) adds to that carbon atom of the unsymmetrical alkene
which is maximum substituted or which possesses lesser number of hydrogen
atoms.

CH3CH＝CH2 + HBr ⟶ CH3-CH(Br)-CH3

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

(7)
 HYDROCARBONS
13

HCl or HI. This reaction is known as peroxide or Kharash effect or addition

reaction anti to Markovnikov rule.

CH3CH＝CH2 + HBr ⟶ CH3-CH2-CH2-Br

iv. Polymerisation: Polymerisation is the process where monomers combines

together to form polymers. The large molecules thus obtained are called
polymers. Other alkenes also undergo polymerisation.

n(CH2＝CH2) ⟶ (-CH2-CH2-)n

)
m
Alkenes

.co
Like alkenes, alkynes are also unsaturated hydrocarbons with general formula CnH2n

la
– 2. They contain at least one triple bond between two carbon atoms. These
have four H-atoms less compared to alkanes. The first stable member of

a
alkyne series is ethyne commonly known as acetylenes.
hs
1. Nomenclature
at
In common system, alkynes are named as derivatives of acetylene. In IUPAC system,
lp

they are named as derivatives of the corresponding alkanes replacing ‘ane’ by

ita

the suffix ‘yne’. The position of the triple bond is indicated by the first triply
bonded carbon. Common and IUPAC names of a few members of alkyne
ig

series are given in the table below:

.d
w

S.No. Structure IUPAC Name

w
(w

1. C2H2 Ethyne

2. C3H4 Propyne

3. C4H6 Butyne

4. C5H8 Pentyne

5. C6H10 Hexyne

(8)
 HYDROCARBONS
13

2. Preparation

i. From calcium carbide: On industrial scale, ethyne is prepared by reacting

calcium carbide with water. Calcium carbide is prepared by heating quick lime
with coke. Quick lime can be obtained by heating limestone as shown in the
following reactions:

CaCO3 ⟶ CaO + CO2

CaO + 3C ⟶ CaC2 + CO

)
m
CaC2 + 2H2O ⟶ Ca(OH)2 + C2H2

.co
ii. From vicinal dihalides: Vicinal dihalides on treatment with alcoholic
potassium hydroxide undergo dehydrohalogenation. One molecule of

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hydrogen halide is eliminated to form alkenyl halide which on treatment with
sodamide gives alkyne.

a
CH2(Br)-CH2(Br) + KOH ⟶ CH2＝CH2 ⟶ CH☰CH
hs
at
4. Properties of Alkenes
lp

I. Physical properties
ita

i. The first three members (acetylene, propyne and butynes) are gases, the next
ig

eight are liquids and higher ones are solids.

.d

ii. All alkynes are colourless. All alkynes except ethyne which have an offensive
w

characteristic odour, are odourless.

w

iii. Alkynes are weakly polar in nature and nearly insoluble in water. They are
quite soluble in organic solvents like ethers, carbon tetrachloride and
(w

benzene.
iv. Their melting point, boiling point and density increase with increase in molar
mass.

II. Chemical properties

i. Addition of dihydrogen: Alkynes contain a triple bond, so they add up, two
molecules of dihydrogen.

CH☰CH + H2 ⟶ CH2＝CH2 ⟶ CH3-CH3

ii. Addition of halogens: Alkynes contain a triple bond, so they add up, two

(9)
 HYDROCARBONS
13

molecules of halogen.

CH☰CH + Cl2 ⟶ CH(Cl)＝CH(Cl) ⟶ CH(Cl)2-CH(Cl)2

iii. Addition of hydrogen halides: Two molecules of hydrogen halides (HCl, HBr,
HI) add to alkynes to form gemdihalides (in which two halogens are attached
to the same carbon atom).

CH☰CH + HCl ⟶ CH2＝CH(Cl)

)
iv. Addition of water: Like alkanes and alkenes, alkynes are also immiscible and

m
do not react with water. However, one molecule of water adds to alkynes on
warming with mercuric sulphate and dilute sulphuric acid at 333K to form

.co
carbonyl compounds.

la
CH☰CH + H2O ⟶ CH3-CHO

a
v. hs
Polymerisation: Ethyne on passing through red hot iron tube at 873K
undergoes cyclic polymerization. Three molecules polymerise to form
at
benzene, which is the starting molecule for the preparation of derivatives of
benzene, dyes, drugs and large number of organic compounds.
lp
ita
ig
.d
w
w
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vi. Oxidation:

2C2H2 + 5O2 ⟶ 4CO2 + 2H2O

Aromatic Hydrocarbon
Aromatic hydrocarbons are also known as ‘arenes’. Since most of them possess
pleasant odour (Greek; aroma meaning pleasant smelling), the class of
compounds are known as ‘aromatic compounds’. Most of the compounds are
found to have benzene ring. Benzene ring is highly unsaturated and in a
majority of reactions of aromatic compounds, the unsaturation of benzene
ring is retained. Aromatic compounds containing benzene ring are known as

(10)
 HYDROCARBONS
13

benzenoids and those, not containing a benzene ring are known as non-
benzenoids.
1. Nomenclature
Since all the 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 which differ in the position of
substituents. So we can say that disubstituted products of benzene show
position isomerism. The three isomers obtained are 1, 2 or 1, 6 which is

)
known as the ortho (o-), the 1, 3 or 1, 5 as meta (m-) and 1, 4 as para (p-)

m
disubstitued compounds.

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a la
hs
at
lp

2. Structure
ita

The molecular formula of benzene, C6H6, indicates a high degree of unsaturation. All
the six carbon and six hydrogen atoms of benzene are identical. On the basis
ig

of this observation August Kekule in 1865 proposed the following structure

.d

for benzene having cyclic arrangement of six carbon atoms:

w
w
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3. Resonance
Even though the double bonds keep on changing their positions. The structures
produced is such that the position of nucleus remains the same in each of the
structure. The structural formula of such a compound is somewhat
intermediate (hybrid) between the various propose formulae. This state is
known as Resonance.

(11)
 HYDROCARBONS
13

)
m
4. Preparation of Benzene

.co
i. Cyclic polymerisation of ethyne: Ethyne on passing through red hot iron tube
at 873K undergoes cyclic polymerization.

a la
hs
at
lp
ita

ii. Decarboxylation of aromatic acids: Sodium salt of benzoic acid i.e., sodium
ig

benzoate on heating with sodalime gives benzene.

.d
w
w
(w

iii. Decarboxylation of aromatic acids: Sodium salt of benzoic acid i.e., sodium
benzoate on heating with sodalime gives benzene.

(12)
 HYDROCARBONS
13

iv. Reduction of phenol: Phenol is reduced to benzene by passing its vapour over
heated zinc dust.

5. Properties of Benzene

I. Physical Properties

)
m
i. Aromatic hydrocarbons are non-polar molecules and are usually colourless

.co
liquids or solids with a characteristic aroma.
ii. The napthalene balls used in toilets and for preservation of clothes because of

la
unique smell of the compound.

a
iii. Aromatic compounds are insoluble in water but soluble in organic solvents
hs
such as alcohol and ether.
at
iv. They burn with sooty flame.
lp

II. Chemical properties

ita

i. Nitration: A nitro group is introduced into the benzene ring when benzene is
ig

heated with a mixture of concentrated nitric acid and concentrated sulphuric

acid.
.d
w
w
(w

ii. Halogenation: Arenes undergo halogenation when it is treated with halogens

in presence of Lewis catalyst such as anhy. FeCl3, FeBr3 or AlCl3 to yield
haloarenes.

(13)
 HYDROCARBONS
13

iii. Sulphonation: The replacement of a hydrogen atom by a sulphonic acid group

in a ring is called sulphonation. It is carried out by heating benzene with
fuming sulphuric acid or oleum (conc. H2SO4 + SO3).

)
m
iv. Friedel-Crafts alkylation reaction: When benzene is treated with an alkyl
halide in the presence of anhydrous aluminium chloride, alkylbenzene is

.co
formed.

a la
hs
at
Activating Groups: Electron donating groups (EDG, +M, +I, +H. C. effect) in the
lp

benzene ring will more stabilize the σ-complex (Arenium ion complex) with
ita

respect to that of benzene and hence they are known as activator.

ig

Deactivating Groups: Electron drawing groups (–M, –I effects) will destabilize σ-

complex as compared to that of benzene. Therefore substituted benzenes
.d

where substituents are electron withdrawing decreases reactivity towards SE

w

reactions.
w

Summary-
(w

1. Hydrocarbons: The compounds which are made up of only carbon and

hydrogen elements.
2. LPG (Liquefied petroleum gas), LNG (Liquefied natural gas) and CNG
(Compressed natural gas) are important fuels.
3. Alkanes are saturated hydrocarbons having general formula CnH2n+2. They
contain only C—C and C—H sigma bonds.
4. Alkenes are unsaturated hydrocarbons having general formula CnH2n. They
contain a carbon-carbon double bond.
5. Alkynes are unsaturated hydrocarbons having general formula CnH2n–2. They

(14)
 HYDROCARBONS
13

contain a carbon-carbon triple bond.

6. Alkanes exhibit conformational isomerism due to almost free rotation about
C—C sigma bond.
7. Alkenes exhibit geometric isomerism due to restricted rotation about carbon-
carbon double bond.
8. The cis isomer is more polar and has higher boiling point than the trans
isomer. On the other hand the melting point of trans isomer is higher.
9. Cracking: The process of decomposing higher hydrocarbons into lower

)
hydrocarbons by strong heating.

m
10. Reforming or Aromatisation: The process of converting aliphatic and alicyclic

.co
hydrocarbons into aromatic hydrocarbons by heating in the presence of
suitable catalysts such as platinum.

la
11. Grignard reagent: RMgX, Alkyl magnesium halide.

a
12. Soda-lime decarboxylation of sodium salts of carboxylic acids leads to
hs
formation of alkane with one carbon less than the starting compound.
at
13. Dehydrohalogenation of Alkyl halides is carried out by heating with alcoholic
lp

solution of KOH.
ita

14. Branched chain hydrocarbons have lower boiling points than straight chain
hydrocarbons having same number of carbon atoms.
ig

15. Among isomeric xylenes, para isomer has the highest melting point.
.d

16. Baeyer’s reagent: 1% cold and alkaline solution of KMnO4.

w

17. Markovnikov’s rule: During electrophilic addition across unsymmetrical

w

double bond, the negative part of the adding molecule goes to that carbon
which has less number of hydrogen atoms.
(w

18. Kharash effect: Anti-Markovnikov addition of HBr to alkenes in the presence

of organic peroxides.
19. Arenes are aromatic hydrocarbons. They contain at least one benzene ring.
20. The important reactions of alkanes are free radical substitution reactions
while that of alkenes and alkynes are electrophilic addition reactions.
21. Aromatic hydrocarbons are undergo mainly electrophilic substitution
reactions inspire of high degree of unsaturation present in them.
22. Aromaticity in aromatic compounds is due to the presence cyclic, delocalized
system of (4n+2) π electrons.

(15)
 HYDROCARBONS
13

23. Substitution reactions are common for alkanes and arenes whereas addition
reactions are common for alkenes and alkynes.
24. The catalyst for Friedel-Craft reaction is anhydrous AlCl3.
25. Terminal alkynes are acidic in character.
26. Electron releasing groups increase the reactivity of benzene ring towards
electrophilic substitution reactions. Some examples are —R, —OH, —NH2, —
OR, —NHCOCH3, etc.

)
m
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a la
hs
at
lp
ita
ig
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w
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(16)
 13
HYDROCARBONS

(w
w
w
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ig
ita
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hs
ala
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(17)
 HYDROCARBONS
13

Important Questions

Multiple Choice questions-

Question 1. Which of the following compounds will exhibit geometrical isomerism?
(a) 1 – Phenyl – 2 – butene
(b) 3 – Phenyl – 1 – butene
(c) 2 – Phenyl – 1 butene

)
m
(d) 1, 1 – Diphenyl – propene.

.co
Question 2. Hydrocarbon containing following bond is most reactive
(a) C ≡ C

la
(b) C = C

a
(c) C – C hs
(d) All of these
at
Question 3. A gas decolourised by KMno4 solution but gives no precipitate with
lp

ammoniacal cuprous chloride is

ita

(a) Ethene
(b) Propane
ig

(c) Propene
.d

(d) Methane
w

Question 4. A dibromo derivative of an alkane reacts with sodium metal to form an

w

alicyclic hydrocarbon. The derivative is _______

(w

(a) 1, 4-dibromobutane
(b) 1, 2-dibromoethane
(c) Carbon
(d) None of the above
Question 5. Reaction of HBr with propene in the presence of peroxide gives:
(a) 3 – Bromo propane
(b) Allyl bromide
(c) n – Propyl bromide
(d) Isoproyl bromide

(18)
 HYDROCARBONS
13

Question 6. Which branched chain isomer of the hydrocarbon with molecular mass
72u gives only one isomer of mono substituted alkyl halide?
(a) Neopentane
(b) Carbon
(c) Isohexane
(d) Neohexane
Question 7. Aromatic compounds burn with a sooty flame because?

)
(a) They have a ring structure of carbon atoms

m
(b) They have a relatively high percentage of hydrogen

.co
(c) They have a relatively high percentage of carbon
(d) They resist reaction with oxygen of air

la
Question 8. The lowest alkene, that is capable of exhibiting geometrical isomerism is

a
(a) Ethene hs
at
(b) But – 1- ene
(c) But – 2 – ene
lp

(d) Propene
ita

Question 9. Which one of these is NOT TRUE for benzene?

ig

(a) Heat of hydrogenation of benzene is less than the theoretical value

.d

(b) There are three carbon-carbon single bonds and three carbon-carbon double
w

bonds
w

(c) It forms only one type of monosubstituted product

(w

(d) The bond angle between carbon-carbon bonds is 120o

Question 10. Ethyl benzene cannot be prepared by _____.
(a) Wurtz Reaction
(b) Wurtz Fittig reaction
(c) Clemmensen Reduction
(d) Carbon
Question 11. Propyne on polymerization yields
(a) Mesitylene
(b) Benzene

(19)
 HYDROCARBONS
13

(c) Ethyl benzene

(d) Propyl benzene.
Question 12. A gas decolourised by KMno4 solution but gives no precipitate with
ammoniacal cuprous chloride is
(a) Ethene
(b) Propane
(c) Propene

)
(d) Methane

m
Question 13. Among the following compounds the one that is most reactive towards

.co
electrophilic nitration is
(a) Toluene

la
(b) Benzene

a
(c) Benzoic Acid hs
(d) Nitrobenzene
at
Question 14. HBr reacts with CH2 = CH – OCH3 under anhydrous conditions at room
lp

temperature to give
ita

(a) CH3CHO and CH3Br

(b) BrCH2CHO and CH3OH
ig

(c) BrCH2 – CH2 – OCH3

.d

(d) H3C – CHBr – OCH3

w

Question 15. The angle strain in cyclobutane is

w

(a) 24°44
(w

(b) 29°16
(c) 19°22
(d) 9°44

Very Short:
1. Give different isomers of C4H10 with their I.U.P.A.C. names.
2. Give the I.U.P.A.C. name of the lowest molecular weight alkane that contains a
quaternary carbon.
3. Which of the following has the highest boiling point?

(20)
 HYDROCARBONS
13

(i) 2-methylpentane
(ii) 2, 3 – dimethylbutane
(iii) 2, 2-dimethylbutane.
4. Give the structure of the alkene (C4H8) which adds on HBr in the presence and in
the absence of peroxide to give the same product C4H9Br.
5. How will you separate propene from propyne?
6. Name two reagents that can be used to distinguish \ between ethene and ethyne.

)
7. How will you detect the presence of unsaturation in an organic compound?

m
8. Arrange the following In order of increasing volatility: gasoline, kerosene, and

.co
diesel.
9. Arrange the following: HCl, HBr, HI, HF in order of decreasing reactivity towards

la
alkenes.

a
10. Out of ethylene and acetylene which is more acidic and why?
hs
Short Questions:
at
lp

1. What are the various products expected when propane reacts with fuming
nitric acid?
ita

2. What is aromatization? How will you convert ^hexane into benzene?

ig

3. Give the different conformations of ethane with their

.d

(i) Sawhorse representation and

w

(ii) Newmann Projection formulae.

w

4. What are the relative stabilities of different conformations of ethane? Is it

(w

possible to isolate these at room temperature?

5. What is Saytzeff Rule? What are the expected products when 2-Bromobutane
is dehydrohalogenation with ale. KOH?
6. Define Markownikov rule. Explain it with an example.

Long Questions:
1. Alkynes are less reactive than alkenes towards addition reaction even though
they contain 2-7t bond. Give reason.
2. Why do addition reactions occur more readily with alkenes & alkynes than with
aromatic hydrocarbons?

(21)
 HYDROCARBONS
13

3. A Hydrocarbon A,ss adds one mole of hydrogen in presence of platinum

catalyst from n-Hexane. When A is oxidized vigorously with KMnO4, a single
carboxylic acid, containing three carbon atoms is isolated. Give the structure of
A & explain.
4. How would you carry out the following conversion?
5. How would you convert the following compounds to benzene?
(i) Acetylene
(ii) Benzoic acid

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(iii) Hexane
(iv) Benzene diazonium chloride

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Assertion Reason Questions:

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1. In the following questions, a statement of Assertion (A) followed by a
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statement of Reason (R) is given. Choose the correct option out of the choices
given below each question.
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Assertion (A) : Toluene on Friedel Crafts methylation gives o– and p–xylene.
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Reason (R) : CH3-group bonded to benzene ring increases electron density

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at o– and p– position.
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(i) Both A and R are correct and R is the correct explanation of A.

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(ii) Both A and R are correct but R is not the correct explanation of A.
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(iii) Both A and R are not correct.

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(iv) A is not correct but R is correct.

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2. In the following questions, a statement of Assertion (A) followed by a

statement of Reason (R) is given. Choose the correct option out of the choices
given below each question.

Assertion (A) : Nitration of benzene with nitric acid requires the use of
concentrated sulphuric acid.
Reason (R) : The mixture of concentrated sulphuric acid and concentrated
nitric acid produces the electrophile, NO2
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.

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 HYDROCARBONS
13

(iii) Both A and R are not correct.

(iv) A is not correct but R is correct.
Case Study Based Question:
1. Compound (A) is an important industrial feed stocks, but it’s largest use as the
fuel for the oxyacetylene torch. It is a colourless, foul smelling gas that burns in
air with a yellow, sooty flame.

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(1) Identify the product A.

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(a) Ethane hs
(b) Ethyne
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(c) Ethene
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(d) Methane
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(2) The compound (B) formed is:

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(a) Cyclohexane
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(b) Benzene
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(c) Hexane
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(d) Cyclopentane.
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(3) The product E is:

(a) Nitrobenzene
(b) Benzene sulphonic acid
(c) Both (a) and b
(d) None of these.
(4) Identify the product ‘D’.
(a) Chlorobenzene
(b) Bromobenzene
(c) Toluene

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 HYDROCARBONS
13

(d) Acetophenone

Answer Key:
MCQ
1. (a) 1 – Phenyl – 2 – butene

2. (a) C = C

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3. (a) Ethene

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4. (a) 1, 4-dibromobutane

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5. (c) n – Propyl bromide

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6. (a) Neopentane

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7.
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(c) They have a relatively high percentage of carbon
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8. (c) But – 2 – ene
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9. (b) There are three carbon-carbon single bonds and three carbon-carbon
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double bonds
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10. (a) Wurtz Reaction

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11. (a) Mesitylene

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12. (a) Ethene

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13. (a) Toluene

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14. (d) H3C – CHBr – OCH3

15. (d) 9°44

Very Short Answer:

1.

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 HYDROCARBONS
13

2.

It is and its I.U.P.A.C. name is 2, 2-Dimethylpropane.

3. (i) 2—methyl pentane has the largest surface area and hence has the highest

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boiling point.

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4. 2-Butene with structure CH3 – CH = CH — CH3 being symmetrical gives the same
product, i.e., 2-bromobutane CH3 CH (Br) CH2CH3.

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5. Bypassing the mixture through ammoniacal AgNO3 solution when propyne reacts

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while propene passes over. hs
6. Tollen’s reagent | Ammoniacal AgNO3 | and amm. CuCl solution.
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7. Either by Baeyer’s reagent

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or by Br, in CC14.
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8. Diesel, kerosene, gasoline.

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9. HF, HCl, HBr, HI..

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10. Acetylene. Ethylene and acetylene have sp2, sp hybridized C atoms respectively.
Due to the 50% S character of the C – H bond of acetylene rather than the 33%
S-Character of the C – H bond in ethene, acetylene is more acidic.

Short Answer:
Ans: 1

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 HYDROCARBONS
13

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Ans: 2. Aromatization. It is the process that involves cyclization, isomerization, and
dehydrogenation with the application of heat and catalyst to convert alkanes

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containing six or more carbon atoms into aromatic hydrocarbons.

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Ans: 3. Sawhorse representation Newmann projection models

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Ans: 4. The staggering form of ethane is more stable than the eclipsed form because
the force of repulsion between hydrogen atoms on adjacent C atoms is
minimum. The energy difference between the staggered form and eclipsed
form of ethane is just 12.55 kJ mol-1. Therefore, it is not possible to separate
these two forms of ethane at room temperature.

(26)
 HYDROCARBONS
13

Ans: 5. The staggering form of ethane is more stable than the eclipsed form because
the force of repulsion between hydrogen atoms on adjacent C atoms is
minimum. The energy difference between the staggered form and eclipsed
form of ethane is just 12.55 kJ mol-1. Therefore, it is not possible to separate
these two forms of ethane at room temperature.

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Ans: 6. Markownikov rule states. The negative part of the addendum adding to an
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unsymmetric alkene goes to that C atom of the double bond which is attached
to a lesser number of C atoms.
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Long Answer:
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Ans: 1. This is due to

1. greater electronegativity of sp-hybridized carbon of alkynes than sp2 hybridized

carbon atoms of alkenes which holds the π-electrons of alkynes more tightly
and

2. greater delocalization of π-electrons in alkynes (because of the cylindrical

nature of their n electron cloud) than in alkenes. As a result, n electrons of
alkynes are less easily available for addition reactions than those of alkenes.

Consequently, alkynes are less reactive than alkenes towards addition reactions.

(27)
 HYDROCARBONS
13

Ans: 2. The energy gained by forming two sigma bonds (of four sigma bonds) more
than compensates for the loss of one or two n bonds when addition occurs to
an alkene or alkyne. However, in aromatic hydrocarbons, the aromatic ring is
specially stabilized by the delocalization of n electrons about the ring.

It, therefore, requires substantial activation energy to cause the loss of its aromatic
character. The most usual reaction in arenes is thus substitution rather than
addition, since substitution does not result in loss of aromatic character.

Ans: 3.

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1. Since hydrocarbon A adds one molecule of H2 in presence of platinum to form

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n-hexane. A must be a hexene.

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2. Since A on vigorous oxidation with KMnO4 gives a single carboxylic acid
containing three carbon atoms, therefore, A must be asymmetrical hexene i.e.

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hex-3-ene. hs
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Thus, the given hydrocarbon A is hex-3-ene.

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Ans: 4. Propene to Ethyne

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Ans: 5. (i) Acetylene into benzene. Ethyne (Acetylene) in passing through a red hot

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 HYDROCARBONS
13

iron tube at 873 K undergoes cyclic polymerization as shown below.

(ii) Benzoic acid into benzene

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(iii) Hexane into benzene

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(iv) Benzene diazonium chloride into benzene

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 HYDROCARBONS
13

Assertion Reason Answer:

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1. (i) Both A and R are correct and R is the correct explanation of A.

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2. (i) Both A and R are correct and R is the correct explanation of A.

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Case Study Answer:

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1. Answer: hs
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(1) (b) Ethyne
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(2) (c) Hexane

(3) (b) Benzene sulphonic acid
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(4) (d) Acetophenone

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(30)
CHEMISTRY

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CHAPTER 14: ENVIRONMENTAL CHEMISTRY

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 ENVIRONMENTAL CHEMISTRY
14

ENVIRONMENTAL CHEMISTRY

Introduction

Interrelation of biological, social, economical, physical and chemical studies with our
surrounding is called environmental studies. Environmental pollution is the greatest health
hazard all over the world. Environmental chemistry deals with the study of the origin,
transport, reactions, effects and fates of chemical species in the environment.

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An undesirable change in physical, chemical or biological characteristics of air, water and
land that is harmful to human life and other living organisms, living conditions, cultural

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assets, industrial progress and harms our resources is called pollution.

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Environmental Pollution

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Undesirable changes that have harmful effects on plants, animals and human beings in our
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surrounding is called environmental pollution.
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Pollutant
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The substance which causes pollution and is harmful for environment is called pollutant.
Pollutants are of two types:
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1. Biodegradable
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Those substances which are degraded rapidly by natural process or artificial methods are
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called biodegradable pollutants. Ex- discarded vegetables.

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2. Non-biodegradable
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Those substances which degrade at very slow rate or does not degrade by natural biological
process, for example, DDT, arsenic salts of heavy metals, radioactive materials and plastics
are non-biodegradable pollutants.

Atmospheric Pollution

Lowest layer of atmosphere is troposphere which have dust, water vapour and clouds, it
contains dust, water vapour and clouds while stratosphere contains ozone. Atmospheric
pollution includes both troposphere and stratosphere pollution.
Tropospheric Pollution
Tropospheric pollution occurs due to the presence of undesirable solid or gaseous particles

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 ENVIRONMENTAL CHEMISTRY
14

in the air.
1. Gaseous air pollutants:
i. Oxides of Sulphur: Oxides of sulphur are produced when sulphur containing fossil
fuel is burnt. The most common species, sulphur dioxide, is a gas that is poisonous
to both animals and plants. It has been reported that even a low concentration of
sulphur dioxide causes respiratory diseases e.g., asthma, bronchitis, emphysema in
human beings. Sulphur dioxide causes irritation to the eyes, resulting in tears and
redness.
2SO2 + O2 ⟶ 2SO3

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ii. Oxides of Nitrogen: Mainly produced by combustion of fossil fuels at high

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temperature in automobile engines mainly NO and NO2.

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These produce reddish brown haze or brown air NO2 is more dangerous than NO.
These oxides can cause pulmonary oedema, dilation of arteries, eye irritation, heart

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problems, injury to liver and kidneys and also causes acid rains.

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N2 + O2 ⟶ 2NO hs
2NO + O2 ⟶ 2NO2
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iii. Hydrocarbons: Produced naturally (e.g., marsh gas) as well as due to incomplete
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combustion. These are carcinogenic and causes irritation of mucous membrane,

eyes. They causes ageing, breakdown of tissues, shedding of flower, leaves and
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twigs in plants.
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iv. Carbon monoxide: It is colourless, odourless gas. It is produced by incomplete

combustion of fuels, naturally it is produced by oceans or by decaying of organic
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matter by bacteria. It is poisonous because it combines with hemoglobin to form

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300 more times stable carboxyhemoglobin which reduces oxygen-carrying capacity

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of blood and results into giddiness, headache, decreased vision, cardiovascular

malfunction and asphyxia. Cigarette smoke also contains a lot of CO which induces
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premature birth deformed babies and spontaneous abortions in pregnant women.

v. Carbon dioxide: It is produced naturally by volcanic eruptions, respiration. It is also
produced by burning of fossil fuels. Increased level of CO2 is controlled by green
plants during photosynthesis. It is a greenhouse gas and responsible for global
warming. It causes headache nausea and asphyxiation.
2. Greenhouse Effect
This effect was discovered by Fourier and the term was coined by Arrhenius. 75% of
solar radiation is absorbed by earth surface and remaining is reflected back. Some of
which is absorbed by greenhouse gases such as carbon dioxide, methane, ozone,
chlorofluorocarbon compounds (CFCs) and water vapour in the atmosphere which

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 ENVIRONMENTAL CHEMISTRY
14

increases temperature of atmosphere is called greenhouse effect.

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3. Acid Rain

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When the pH value of the rain water drops below 5.6, it is known as acid rain. Acid

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rain is a byproduct of a variety of human activities that emit the oxides of sulphur and
nitrogen in the atmosphere.
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2SO2(g) + O2(g) + 2H2O(l) ⟶ 2H2SO4(aq)

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Stratospheric Pollution
1. Ozone Hole
Depletion in the concentration of ozone over a restricted area as over Antarctica is
called ozone hole. Stratospheric clouds are formed over Antarctica.
Molecular oxygen splits into free oxygen atoms by UV radiations which combine with
molecular oxygen to form ozone.
O2(g) ⟶ [O](g) + [O](g)
[O](g) + O2(g) ⟶ O3(g)
As ozone is thermodynamically unstable hence, there exists dynamic equilibrium

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 ENVIRONMENTAL CHEMISTRY
14

between its decomposition and formation. Ultraviolet radiations dissociate

chlorofluorocarbon to give chlorine-free radical, which combines with ozone to form
chlorine monoxide radical which combines with free oxygen to form more chlorine-
free radicals.
CF2Cl2 ⟶ [C]F2Cl + [Cl]
[Cl] + O3 ⟶ Cl[O] + O2
2Cl[O] + O3 ⟶ 2[Cl] + 2O2
Effects of Depletion of The Ozone Layer:
Bad ozone is formed in troposphere that harms plants and animals while good ozone

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is formed in stratosphere which acts as shield. UV rays can enter in earth’s
atmosphere.

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• It is harmful as can cause skin cancer.

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• It increases transpiration hence decreases soil moisture.

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• It damages paints and fibres, causing them to fade faster.
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Water Pollution
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Any unwanted change which detiorate quality of water and make it unfit for drinking is
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called water pollution. Pollution of water originates from human activities.

Causes of Water Pollution

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1. Organic matter such as leaves, grass, trash etc. as well as excessive phytoplankton growth
in water causes water pollution as this matter is decomposed through microbial activity is
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known as putrescibility which requires oxygen. Degree of impurity of water due to

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organic matter is measured in terms of Biochemical Oxygen Demand (BOD).

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2. Pathogens: Disease-causing agents are called pathogens e.g., viruses, bacteria, protozoa,
helminthes, algae etc. Human excreta contains E.coli and Streptococcus faecalis bacteria
which cause gastrointestinal diseases.

3. Chemical pollutants: These are of two types, inorganic and organic.

4. Inorganic pollutants constitute acids, salts, heavy metals such as Cd, Hg, Ni etc. Heavy
metals can damage central nervous system, liver and kidneys.

5. Organic pollutants constitute, pesticides, petroleum pollutants, PCBs, detergents,

fertilizers etc. PCBs (Polychlorinated Biphenyls) are carcinogenic and phosphatic fertilizers
increase algae growth. Acidic water is harmful for aquatic life as well as for drinking.

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 ENVIRONMENTAL CHEMISTRY
14

Soil Pollution
It is unfavourable alteration of soil by addition or removal of substances and factors which
decrease soil productivity, quality of plants and ground water is called soil pollution. Mainly
caused by chemicals added into soil as pesticides, herbicides and fertilizers for better
productivity.

Causes of Soil Pollution

1. Pesticides: These are actually synthetic toxic chemicals with ecological repercussions.
These are used in killing pathogens, pests and in inhibiting unwanted growth in

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agriculture, horticulture, forestry and water.

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2. Fertilizers: Excessive use of fertilizers decreases natural microflora hence detiorate soil.

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Therefore, now a days organic farming is encouraged which involves organic pesticides,
biofertilizers and disease resistant varieties.

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3. Industrial wastes: These are both solid and liquid and are dumped over the soil. These
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contain toxic chemicals like mercury, copper, zinc, lead, cadmium, cyanides, acid, alkalies
etc.
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Strategies to Control Environmental Pollution

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Two sources of environment pollutant are household waste and industrial waste. Following
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method can be used to control them.

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1. Recycling: Waste are recycled into manufacturing of new material. For example, scrap iron,
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broken glass, clothes can be made from recycled plastic waste and soon becomes available
in market. We can also recover energy from burning combustible waste.
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2. Digestion: Waste material can be degraded by anaerobic micro-organisms in absence of

air. It can be used to produce electricity. First biodegradable and non-biodegradable waste
are separated then biodegradable wastes are mixed with water and cultured by bacterial
species which produce methane.

3. Dumping: Sewage sludge acts as fertilizer because it contains nitrogen and phosphorus
hence, it is dumped in land areas which increases soil fertility.

Green Chemistry
Green chemistry is a way of thinking and is about utilizing the existing knowledge and
principles of chemistry and other sciences to reduce the adverse impact on environment.

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 ENVIRONMENTAL CHEMISTRY
14

Utilization of existing knowledge base for reducing the chemical hazards along with the
development activities are the foundation of green chemistry.

Summary-
1. Environmental pollution causes undesirable changes in our surrounding that have
harmful effect on plants, animals and human beings.
2. Atmospheric pollution is studied as tropospheric pollution and stratospheric pollution.
3. Smog and global warming take place due to tropospheric pollution.

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4. Stratospheric pollution causes depletion of ozone layer.

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5. Water pollution is caused by pathogens, organic wastes and chemical pollutants.

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6. Soil pollution is caused by insecticides, pesticides and herbicides.
7. Industrial waste is of two type, biodegradable and non-biodegradable.

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8. Green chemistry is a way of thinking and is about to utilize the existing knowledge and

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principles of chemistry and other sciences to reduce the adverse impact on
environment.
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 ENVIRONMENTAL CHEMISTRY
14

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(7)
 ENVIRONMENTAL CHEMISTRY
14

Important Questions

Multiple Choice questions-

1. Photochemical smog normally does not contain
(a) Chlorofluorocarbons
(b) Peroxyacetyl nitrate
(c) Ozone

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(d) Acrolein

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2. Depletion of the ozone layer is caused due to
(a) Ferrocene

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(b) Fullerenes

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(c) Freons hs
(d) Polyhalogens
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3. Find the incorrect statement
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(a) BOD value of clean water is less than 5 ppm

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(b) Drinking water pH should be between 5.5-9.5

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(c) carbon, sulphur and nitrogen oxides are the most widespread air pollutants
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(d) dissolved oxygen concentration below 5 ppm is ideal for the growth of fish
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4. Find the secondary pollutant among these

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(a) PAN
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(b) N2O
(c) SO2
(d) CO2
5. The reaction responsible for the radiant energy of the Sun is
(a) nuclear fission
(b) nuclear fusion
(c) chemical reaction
(d) combustion

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 ENVIRONMENTAL CHEMISTRY
14

6. Alum’s capacity to purify water is due to

(a) softens hard water
(b) pathogenic bacteria get destroyed
(c) impurities’ coagulation
(d) it improves taste
7. The coldest region of the atmosphere
(a) Troposphere

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(b) Thermosphere

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(c) Stratosphere

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(d) Mesosphere

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8. Which of the oxide of nitrogen is not a common pollutant?

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(a) N2O5
(b) N2O
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(c) NO
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(d) NO2
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9. The compound essential for the process of photosynthesis has this element
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(a) Ca
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(b) Ba
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(c) Fe
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(d) Mg
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10. In the air, N2 and O2 occur naturally but they do not react to form oxides of nitrogen because
(a) oxides of nitrogen are unstable
(b) catalyst is required for the reaction
(c) the reaction is endothermic
(d) N2 and O2 do not react with each other
11. This about carbon monoxide is incorrect.
(a) It is produced due to incomplete combustion
(b) The carboxyhaemoglobin (haemoglobin found to CO) is less stable than oxyhaemoglobin

(9)
 ENVIRONMENTAL CHEMISTRY
14

(c) It reduces the oxygen-carrying ability of blood

(d) It forms carboxyhaemoglobin
12. This is a sink for CO
(a) Haemoglobin
(b) Oceans
(c) Micro organisms present in the soil
(d) Plants

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13. DDT is

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(a) Nitrogen containing insecticide

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(b) Biodegradable pollutant

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(c) Non-Biodegradable pollutant

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(d) An antibiotic
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14. Which of the following techniques is/are used in controlling water pollution?
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(a) Reverse osmosis
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(b) Ion exchange process

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(c) Adsorption process

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(d) All of these

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15. Which of the following pollutants cannot be degraded by natural process?

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(a) Heavy metals

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(b) DDT
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(c) Nuclear waste

(d) All of these

Very Short:
1. What is the troposphere?
2. Name some gaseous air pollutants.
3. What are the diseases caused by sulphur dioxide?
4. List gases that are responsible for the greenhouse effect?
5. What is the effect of CFC’s on the ozone layer?
6. What is the greenhouse effect?
7. Which disease is caused due to ozone layer depletion?

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 ENVIRONMENTAL CHEMISTRY
14

8. What is smog?
9. The London smog is caused in which season and time of the day?
10.Name two gases that form acid rain.

Short Questions:
1. What is the role of the ozone layer in the stratosphere?
2. What includes stratospheric pollutants? Give examples.
3. Why is carbon monoxide considered to be poisonous?
4. What are the ill effects of hydrocarbons?

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5. Give one main reason for ozone depletion?

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6. Which zone is called the ozonosphere?
7. What is the ‘greenhouse effect’? How does it affect the global climate?

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Long Questions:
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1. What is the difference between London (classical) smog and photochemical (Los
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Angeles) smog?
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2. Explain how does green house effect cause global warming.

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3. Green plants use carbon dioxide for photosynthesis and return oxygen to the
atmosphere, even then carbon dioxide is considered to be responsible for green
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house effect. Explain why?

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Assertion Reason Questions:

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1. In the following questions a statement of Assertion (A) followed by a statement of

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Reason (R) is given. Choose the correct option out of the choices given below each
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question.

Assertion (A) : Greenhouse effect was observed in houses used to grow plants and these
are made of green glass.
Reason (R) : Greenhouse name has been given because glass houses are made of green
glass.
(i) Both A and R are correct and R is the correct explanation of A.

(ii) Both A and R are correct but R is not the correct explanation of A.

(iii) Both A and R are not correct.

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 ENVIRONMENTAL CHEMISTRY
14

(iv) A is not correct but R is correct.

2. In the following questions a statement of Assertion (A) followed by a statement of

Reason (R) is given. Choose the correct option out of the choices given below each
question.

Assertion (A) : The pH of acid rain is less than 5.6

Reason (R) : Carbon dioxide present in the atmosphere dissolves in rain water and forms
carbonic acid.
(i) Both A and R are correct and R is the correct explanation of A.

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(ii) Both A and R are correct but R is not the correct explanation of A.

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(iii) Both A and R are not correct.

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(iv) A is not correct but R is correct..

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Answer Key:

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MCQ
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1. (a) Chlorofluorocarbons
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2. (c) Freons
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3. (d) dissolved oxygen concentration below 5 ppm is ideal for the growth of fish
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4. (a) PAN
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5. (b) nuclear fusion

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6. (c) impurities’ coagulation

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7. (d) Mesosphere
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8. (a) N2O5
9. (d) Mg
10. (c) the reaction is endothermic
11. (b) The carboxyhaemoglobin (haemoglobin found to CO) is less stable than oxyhaemoglobin
12. (c) Micro organisms present in the soil
13. (c) Non-Biodegradable pollutant
14. (d) All of these
15. (d) All of these

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 ENVIRONMENTAL CHEMISTRY
14

Very Short Answer:

1. The troposphere is the lowest layer of the atmosphere, where humans and other
creatures live. It reaches a height of approximately 10 kilometres above sea level.
2. Sulfur, nitrogen, and carbon oxides, hydrogen sulphide, hydrocarbons, ozone, and other
oxidants are examples of gaseous air pollution.
3. In humans, sulphur dioxide causes respiratory disorders such as asthma, bronchitis, and
emphysema. In addition, sulphur dioxide causes eye irritation, resulting in tears and

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redness.

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4. The gases responsible for the greenhouse effect are: carbon dioxide, methane, water

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vapours, nitrous oxide, CFC’s.

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5. CFC’s also known as chlorofluorocarbons tend to damage the ozone layer and creates
holes in the ozone layer.
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6. The greenhouse effect is the process through which solar energy is absorbed by
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greenhouse gases instead of being reflected back into space. This keeps the earth's
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surface warm and prevents it from freezing.

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7. Skin cancer is caused when the ozone layer is depleted from the atmosphere. The
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ultraviolet rays from the sun reach the earth through the holes present in the ozone layer
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and cause skin related diseases.

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8. Smog is a type of air pollution that was named from the combination of smoke and fog in
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the atmosphere. Smog is created by a mixture of smoke and sulphur dioxide and occurs
when significant amounts of coal are burned in a certain area.
9. The London smog is caused by the hot weather in the summer, especially in the
afternoon.
10. Acid rain is caused by the oxides of sulphur and nitrogen and the gases involved in it are
sulphur dioxide (SO2) and nitrogen dioxide (NO2).

Short Answer:

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 ENVIRONMENTAL CHEMISTRY
14

1. The existence of ozone in the stratosphere blocks 99.5 per cent of the sun's damaging
ultraviolet (UV) light from reaching the earth's surface, shielding people and other animals from
its destructive effects.
2. The outcome of stratospheric pollution is the depletion of the ozone layer in the stratosphere,
which allows dangerous ultraviolet light to reach the earth. This depletion is caused by the
existence of chlorofluorocarbons in the environment.
3. When carbon monoxide is released into the atmosphere, it is inhaled by animals and humans.
Inside the body, carbon monoxide links to haemoglobin to create carboxyl–haemoglobin, which
is 300 times more stable than oxygen –haemoglobin. This oxygen deprivation causes headaches,
blurred vision, anxiety, and cardiovascular problems.

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4. Hydrocarbons are carcinogenic i.e; they cause cancer. Plants are harmed by them because they

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cause ageing, tissue degradation, and the dropping of leaves, flowers, and trigs.

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5. The major cause of ozone layer depletion is chlorofluorocarbons (CFCs). Solvents, spray
aerosols, freezers, and air conditioners, among other things, emit ultraviolet radiation.

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Ultraviolet radiations break down chlorofluorocarbon molecules in the stratosphere, releasing
chlorine atoms.

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6. The ozonosphere is an area or zone in the stratospheric layer of the atmosphere with a high
concentration of ozone gas molecules.
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7. The greenhouse effect is the warming of the planet or global warming caused by the re-
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emission of sun's energy collected by the earth, absorption by CO2 molecules and H2O vapours
existing in the atmosphere near the earth's surface, and then radiation back to the ground.
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Greenhouse affects the climate. If the pace at which solar radiation reaches the earth continues,
the entire global climate will alter dramatically.
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Long Answer:
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1.
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Classical (London) smog Photochemical (Los Angeles) Smog

1. This type of smog was first observed 1. This type of smog was first observed in

in London in 1952. Los Angeles in 1950.

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 ENVIRONMENTAL CHEMISTRY
14

2. It is formed due to the presence of

2. It is formed due to a photochemical
SO2 and humidity in the air which
reaction taking place when the air contains
combines to form H2S04 fog which
NO2 and hydrocarbons.
gets deposited on the particulates.

3. It does not involve any smoke or fog.

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3. It involves smoke and fog.

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The word smog is a misnomer here.

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4. It is formed during the months of

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4. It is formed in the months of winter

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summer during the afternoon when there is
particularly in the morning hours when hs
bright sunlight so that photochemical
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the temperature is low.
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reaction can take place.

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5. It causes a problem in the lungs. 5. It causes irritation in the eyes.

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6. It is reducing in character. 6. It is oxidising in character.

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2. The greenhouse effect is defined as the trapping of the sun’s heat in the lower
atmosphere as a result of increased pollution-causing chemicals such as carbon dioxide.
Water vapour, carbon dioxide (CO2), methane, nitrous oxides, and chlorofluorocarbons
are some of the gases that contribute to the greenhouse effect (CFCs).

The sun’s radiation is partially absorbed by the earth, with the remainder being reflected
back into the atmosphere and escaping. However, greenhouse gases form a blanket in
the atmosphere, trapping radiation and preventing it from leaving. As a result, the earth’s

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 ENVIRONMENTAL CHEMISTRY
14

temperature rises, resulting in global warming.

3. Carbon dioxide is a naturally occurring component of the atmosphere that is essential for
all plant life. It makes up around 0.033 per cent of the atmosphere’s volume. It aids in
maintaining the earth’s temperature, which is necessary for living beings. CO2 balance is
maintained in the atmosphere because CO2 is created by respiration, fossil fuel
combustion, and limestone disintegration, but it is also consumed by plants during
photosynthesis.

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However, human activities have disrupted this equilibrium, and CO2 levels in the

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atmosphere are rising. This is because deforestation has increased by around 25% in the

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last century. The average temperature of the earth has risen by 0.4℃ to 0.8℃ over the

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last approximately 120 years. According to current estimates, a doubling CO2
concentration will result in a temperature increase of between 1.0℃ and 3.5℃. The
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contribution of CO2 to the greenhouse effect is 50%, and the contribution of other trace
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gases is similarly about 50%.

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Assertion Reason Answer:

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1. (iii) Both A and R are not correct.

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2. (ii) Both A and R are correct but R is not the correct explanation of A.
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