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+1 CHEMISTRY NOTES
(FOR THE ACAdEMIC YEAR 2024 - 25)

PREPARED BY:
ANIL KUMAR K L
HSST CHEMISTRY
APHSS ADICHANALLOOR
KOLLAM. PREPARED BY:
ANIL KUMAR K L
Ph: 9496688551
HSST CHEMISTRY
PHSS VANDIPERIYAR
IDUKKI.
Ph: 9496688551
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CONTENTS
No. Unit Page No.

1. Some Basic Concepts of Chemistry 2 – 10

2. Structure of Atom 11 – 24

3. Classification of Elements and Periodicity in 25 – 32

Properties

4. Chemical Bonding and Molecular Structure 33 – 51

5. Thermodynamics 52 – 63

6. Equilibrium 64 - 75

7. Redox Reactions 76 – 82

8. Organic Chemistry - Some Basic Principles and 83 – 102

Techniques

9. Hydrocarbons 103 – 120

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1. SOME BASIC CONCEPTS OF CHEMISTRY

Chemistry is the branch of Science that deals with the preparation, properties,
structure and reactions of material substances.
Some important branches of Chemistry are:
1. Inorganic Chemistry
2. Organic Chemistry
3. Physical Chemistry
4. Analytical Chemistry
5. Polymer Chemistry
6. Biochemistry
7. Medicinal Chemistry
8. Industrial Chemistry
9. Hydrochemistry
10. Electrochemistry
11. Green Chemistry etc.

Matter: Matter is anything that occupies space and has a definite mass. Based on the physical state we
can divide matter into different categories.

1. Solid state
2. Liquid state
3. Gaseous state
4. Plasma state
5. Bose-Einstein condensate
6. Fermionic condensate
7. Quark-Gluon Plasma
In earth crust, matter mainly exists in three physical states – solid state, liquid state and gaseous
state.
In solids, the particles are orderly arranged and they are very close to each other. The particles
cannot move freely. So solids have definite shape and definite volume.
In liquids, the particles are close to each other but they can move around. So, liquids have definite
volume but do not have definite shape.
In gases, the particles are far apart as compared to those present in solid or liquid state and their
movement is easy and fast. So they do not have definite shape and volume. They take the shape of the
container in which they are placed. Also they occupy the complete space of the container in which they
are placed.
The three states of matter are interconvertible by changing the conditions of temperature and
pressure.

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Classification of matter
Based on the chemical composition, matter can be divided into two categories – pure substances and
mixtures.
Pure substances contain only one type of particles. E.g. Sodium (Na), Potassium (K), Hydrogen
(H), Oxygen (O), Helium (He), carbon dioxide (CO2), water (H2O), ammonia (NH3), cane sugar (C12H22O11)
etc.
Pure substances are classified into two – elements and compounds.
Elements are pure substances which contain only one type of atom. The term element was first
introduced by Robert Boyle, the father of ancient Chemistry. Now there are 118 elements starting from
hydrogen (1H) and ending in Oganesson (118Og). Some elements exist as monoatomic, some are diatomic
and some others are polyatomic. E.g. all metals (Sodium, Potassium, Calcium etc) and noble gases
(Helium, Neon etc.) are monoatomic. Hydrogen, Nitrogen, Oxygen etc are diatomic. Phosphorus (P4) and
Sulphur (S8) are polyatomic.
Compounds are pure substances which contain more than one type of atoms. They are formed
by the combination of two or more atoms of different elements in a definite ratio. Their constituents
cannot be separated by physical methods, but they can be separated by chemical methods.
E.g. CO2, H2O, NH3, H2SO4 etc.
Mixtures contain more than one type of particles. The components of a mixture can be
separated by using physical methods like filtration, crystallisation, distillation etc.
E.g. all types of solutions, gold ornaments, sea water, muddy water, air etc.
There are two types of mixtures – homogeneous and heterogeneous mixtures.
Mixtures having uniform composition throughout are called homogeneous mixtures. Here the
components are completely mixed with each other. E.g. all type of solutions, air etc.
Mixtures having different compositions at different parts are called heterogeneous mixtures.
E.g. sea water, soil. Muddy water etc.
Physical and chemical properties
The properties or characteristics of matter can be classified into two types — physical properties
and chemical properties.
Properties which can be measured or observed without changing the composition or identity of the
substance are called physical properties. Measurement of physical properties does not require the
occurrence of a chemical change.
E.g. colour, odour, melting point, boiling point, density, mass etc.
Properties which can be measured only with the occurrence of a chemical change are called chemical
properties. E.g. composition, combustibility, reactivity with acids and bases, etc.
Measurement of physical properties
Any quantitative observation or measurement is represented by a number followed by units in
which it is measured. Earlier, two different systems of measurement were used: the English System and
the Metric System.
Now a days, a common standard system known as International System of Units (SI) is used. This
system has seven base units and they are length, mass, time, electric current, thermodynamic
temperature, amount of substance and luminous intensity. Their SI units are as follows:

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Physical Quantity SI unit & its symbol Electric current ampere (A)
Length metre (m) Thermodynamic temperature kelvin (K)
Mass kilogram (kg) Amount of substance mole (mol)
Time second (s) Luminous intensity candela (cd)
Mass and Weight
Mass is the amount of matter present in a body. It is a constant quantity. Its SI unit is kilogram (kg).
Weight is the gravitational force acting on a body. It is a variable quantity. i.e. it changes with place. Its SI
unit is newton (N).
Volume (V)
It is the amount of space occupied by a body. Its SI unit is m3. In Chemistry, smaller volumes are used.
Hence, volume is often denoted in cm3, dm3, mL, L etc.
1 m3 = 106 cm3 1 L = 103 cm3 (mL) 1cm3 = 1 mL
1 dm3 = 103 cm3 1 dm3 = 1 L
Density (d)
It is the amount of mass per unit volume.
i.e. density = mass/volume. Its SI unit is kg/m3. But it is commonly expressed in g/cm3.
Temperature (T)
It is the degree of hotness or coldness of a body. It is commonly expressed in degree celsius (0C). Other
units are degree fahrenheit (0F), kelvin (K) etc. Its SI unit is kelvin (K).
Degree celsius and degree fahrenheit are related as:
0F
9 0
= ( C) + 32
5
Degree celsius and kelvin are related as:
K = 0C + 273.15 OR, K = 0C + 273
Precision and Accuracy
Precision refers to the closeness of various measurements for the same quantity. But,
accuracy is the agreement of a particular value to the true value of the result.
Scientific Notation
It is an exponential notation in which a number is represented in the form N × 10n, where n is an
exponent having positive or negative values and N is a number (called digit term) which varies between
1.000... and 9.999.....
While writing scientific notation, the value of the exponent ‘n’ becomes positive, when the
decimal is shifted to left and it becomes negative, when the decimal is shifted to right.
E.g. the scientific notation of 368.9 is 3.689 x 102 and that of 0.000563 is 5.63 x 10-4.
Significant Figures
Every experimental measurement has some amount of uncertainty associated with it. 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. 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:
1. All non-zero digits are significant. For example in 285 cm, there are three significant figures and
in 0.25 mL, there are two significant figures.
2. Zeros preceding to first non-zero digit are not significant. Such zero indicates the position of the
decimal point. Thus, 0.03 has one significant figure and 0.0052 has two significant figures.
3. Zeros between two non-zero digits are significant. Thus, 2.005 has four significant figures.

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4. Zeros at the end or right of a number are significant if they are on the right side of the decimal
point; otherwise, they are not significant. For example, 0.200 g has three significant figures.
5. Exact numbers have an infinite number of significant figures. For example, in 2 balls or 20 eggs,
there are infinite significant figures since these are exact numbers and can be represented by
writing infinite number of zeros after placing a decimal i.e., 2 = 2.000000 or 20 = 20.000000
6. In numbers written in scientific notation, all digits are significant. E.g. 4.01×102 has three
significant figures, and 8.256×10–3 has four significant figures.
Rounding off a number to the required number of significant figures
The rules related to rounding off a number are:
1) If the rightmost digit to be removed is more than 5, the preceding number is increased by one.
E.g. 1.386 can be round off to three significant figures, by removing 6. So it becomes 1.39.
2) If the rightmost digit to be removed is less than 5, the preceding number is not changed.
E.g. In 4.334, if 4 is to be removed, then the result is rounded upto 4.33.
3) If the rightmost digit to be removed is 5, then the preceding number is not changed if it is an
even number but it is increased by one if it is an odd number.
For example, if 6.35 is to be rounded by removing 5, we have to increase 3 to 4 giving 6.4 as the
result. But if 6.25 is to be rounded off, it becomes 6.2.

LAWS OF CHEMICAL COMBINATIONS

The combination of elements to form compounds is governed by the following five basic laws:
1. Law of Conservation of Mass (Law of indestructibility of matter): This law was proposed by
Antoine Lavoisier. It states that matter can neither be created nor destroyed. Or, in
a chemical reaction, the total mass of reactants is equal to the total mass of
products. Chemical equations are balanced according to this law.
Illustration
Consider the reaction 2H2 + O2 → 2H2O
Here 4 g of H2 combines with 32 g of O2 to form 36 g of water.
Total mass of reactants = 4 + 32 = 36g
Total mass of products = 36 g
2. Law of Definite Proportions (Law of definite composition): This law was proposed by Joseph
Proust. It states that a given compound always contains exactly the same proportion
of elements by weight. Or, the same compound always contains the same elements
combined in a fixed ratio by mass.
Illustration: Carbon dioxide can be formed in the atmosphere by various methods like respiration,
burning of fuels, reaction of metal carbonates and bicarbonates with acid etc. All these samples of CO 2
contain only two elements Carbon and Oxygen combined in a mass ratio 3:8.
3. Law of Multiple Proportions: This law was proposed by John Dalton. It states that if two
elements can combine to form more than one compound, the different masses of one
of the elements that combine with a fixed mass of the other element, are in small
whole number ratio.
Illustration: Hydrogen combines with oxygen to form two compounds – water and hydrogen
peroxide.
H2 + ½ O2 → H2O
2g 16g 18g
H2 + O2 → H2O2
2g 32g 34g

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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 Lussac’s Law of Gaseous Volumes: This law was proposed by Gay Lussac. It states that
when gases combine to form gaseous products, their volumes are in simple whole
number ratio at constant temperature and pressure.
Illustration: H2 combines with O2 to form water vapour according to the equation 2H2(g) + O2(g) →
2H2O(g). If 100 mL of hydrogen combine with 50 mL of oxygen, we get 100 mL of water vapour.
Thus, the volumes of hydrogen and oxygen which combine together (i.e. 100 mL and 50 mL) bear a
simple ratio of 2:1.
5. Avogadro’s Law: This law was proposed by Amedeo Avogadro. It states that equal volumes
of all gases at the same temperature and pressure should contain equal number of
moles or molecules.
Illustration: If we take 10L each of NH3, N2, O2 and CO2 at the same temperature and pressure, all of
them contain the same number of moles and molecules.
DALTON’S ATOMIC THEORY
The term atom was first used by John Dalton from the Greek word a-tomio (means indivisible).
He proposed the first atomic theory. The important postulates of this theory are:
1. Matter is made up of minute and indivisible particles called atoms.
2. Atoms can neither be created nor be destroyed.
3. Atoms of same element are identical in their properties and mass. While atoms of
different elements have different properties and mass.
4. Atoms combined to form compound atoms called molecules.
5. When atoms combine, they do so in a fixed ratio by mass.
Dalton’s theory could explain the laws of chemical combination.
Atoms and Molecules
Atom is the smallest particle of an element. Molecules are the smallest particle of a substance. A
molecule has all the properties of that substance.
Types of molecules
Based on the type of atoms, molecules are divided into two: homonuclear molecule and
heteronuclear molecule.
A molecule containing only one type of atom is called homonuclear molecule. E.g. H2, O2, N2, O3 (ozone)
etc.
Heteronuclear molecules contain different types of atoms. E.g. CO2, H2O, C6H12O6, NH3 etc.
Based on the no. of atoms there are three types of molecules: monoatomic, diatomic and polyatomic
molecules.
Monoatomic molecules contain only one atom. E.g. all metals, noble gases like He, Ne, Ar etc.
Diatomic molecules contain 2 atoms. E.g. H2, O2, N2, halogens (F2, Cl2, Br2 and I2)
Polyatomic molecules contain more than two atoms. E.g. ozone (O3), Phosphorus (P4), Sulphur (S8) etc.
Atomic mass
Atomic mass (Relative atomic mass) of an element is a number that expresses how many times
the mass of an atom of the element is greater than 1/12th the mass of a C12 atom.
For e.g. atomic mass of Nitrogen is 14, which means that mass of one N atom is 14 times greater
than 1/12th the mass of a C12 atom.
Atomic mass unit (amu): 1/12th the mass of a C12 atom is called atomic mass unit (amu).
1
i.e. 1 amu = 12 x mass of a C12 atom
= 1.66 x 10-24 g = 1.66 x 10-27 kg
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Nowadays, ‘amu’ has been replaced by ‘u’ which is known as unified mass.
Average atomic mass:
Most of the elements have isotopes. So we can calculate an average atomic mass of an element
by considering the atomic mass of the isotopes and their relative abundance. For e.g. chlorine has two
isotopes 35Cl and 37Cl in the ratio 3:1. So the average atomic mass Cl =(3x35 + 1x37)/4 =35.5
Molecular mass:
Molecular mass is the sum of atomic masses of the elements present in a molecule. It is obtained
by multiplying the atomic mass of each element by the number of its atoms and adding them together.
For e.g. molecular mass of H2SO4 is calculated as: 2 x 1 + 32 + 4 x 16 = 98 u.
Formula mass:
In the case of ionic compounds (like NaCl), there is no discrete (separate) molecules. Here the
positive ions and the negative ions are arranged in a three-dimensional structure. So we can calculate
only formula mass by taking molecular formula of the compound.
Mole concept
Mole is the unit of amount of substance. It is defined as the amount of substance that
contains as many particles as there are atoms in exactly 12 g C12 isotope.
1 mole of any substance contains 6.022 x 1023 atoms [602213670000000000000000 atoms]. This
number is known as Avogadro number or Avogadro constant (NA or N0).
1 mol of hydrogen atoms = 6.022×1023 atoms
1 mol of water molecules = 6.022×1023 water molecules
1 mol of sodium chloride = 6.022 × 1023 formula units of sodium chloride
Given mass in gram (w)
No. of moles (n) =
Molar mass (M)
No. of molecules = no. of moles x 6.022 × 1023
Molar mass: The mass of one mole of a substance in gram is called its molar mass (gram
molecular mass). The molar mass in grams is numerically equal to molecular mass in u.
Molar mass of oxygen = 32g
Molar mass of hydrogen = 2g etc.
Molar volume: It is the volume of 1 mole of any substance. At standard temperature and pressure (STP),
molar volume of any gas = 22.4 L (or, 22400 mL). i.e. 22.4 L of any gas at STP contains 1 mole of
the gas or 6.022 x 1023 molecules of the gas and its mass = molar mass.
For e.g. 22.4 L of hydrogen gas = 1 mole of H2 = 6.022x1023 molecules of hydrogen = 2 g of H2
Q1) How many moles of water molecules are present in 180 g of water?
Given mass in gram 180
Ans: No. of moles = = = 10 mol
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 18
Percentage composition
It is the percentage of each element present in 100g of sample of a substance.
Mass of that element in the compound x 100
i.e. Percentage composition of an element =
Molar mass of the compound
Applications: We can check the purity of a given sample of a substance. Also by knowing the percentage
composition, we can calculate the empirical and molecular formula of a compound.
Empirical and Molecular formulae
Empirical formula is the simplest formula of a compound, which gives only the ratio
of different elements present in that compound. But molecular formula is the actual
formula of the compound, that gives the exact number of different elements present in
the sample. For e.g. the empirical formula of glucose is CH2O but its molecular formula is C6H12O6.
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Molecular formula is related to empirical formula by the equation:

Molecular formula (M.F) = Empirical formula (E.F) x n
Molecular mass (MM)
Where n =
Empirical formula mass (EFM)
By knowing the percentage composition, we can calculate the empirical and molecular formula of a
compound as follows:
Q2) An organic compound on analysis gave the following composition. Carbon =
40%, Hydrogen = 6.66% and oxygen = 53.34%. Calculate its molecular formula if
its molecular mass is 180.
Ans:
Element Percentage Atomic mass Percentage Simple ratio Simplest whole
Atomic mass no. ratio
C 40 12 40/12 = 3.33 3.33/3.33 = 1 1
H 6.66 1 6.66/1 = 6.66 6.66/3.33 = 2 2
O 53.34 16 53.34/16 = 3.33 3.33/3.33 = 1 1
Empirical Formula = CH2O
Empirical Formula Mass (EFM) = 12+2+16 = 30
Molar mass (MM) = 180
n = MM/EFM = 180/30 = 6
Molecular formula = Empirical formula x n = (CH2O) x 6 = C6H12O6
Stoichiometry and Stoichiometric calculations
The word ‘stoichiometry’ is derived from two Greek words – stoicheion (meaning element) and
metron (meaning measure). Thus stoichiometry deals with the calculations involving the masses or the
volumes of reactants and the products.
Chemical Equation
It is the representation of a chemical reaction by symbols and formulae. Here the reactants are
written in the left-hand side and the products, on the right-hand side. (The substances which participate
in a chemical reaction are called reactants and the substances which are formed as a result of a reaction
are called products).
A chemical equation should be balanced and the physical states of reactants and products are
written in brackets.
The following information are obtained from a chemical equation.
1. An idea about the reactants and products and their physical states.
2. An idea about the masses of reactants and products.
3. An idea about the number moles and molecules of reactants and products.
4. An idea about the volumes of reactants and products at STP.
Limiting reagent (Limiting reactant)
The reagent which limits a reaction or the reagent which is completely consumed in
a chemical reaction is called limiting reagent or limiting reactant.
For e.g. in the reaction:
2SO2(g) + O2(g) → 2 SO3(g),
2 moles of SO2 reacts completely with 1 mole of O2 to form 2 moles of SO3. If we take 10 moles each of
SO2 and O2, we get only 10 moles of SO3 because 10 moles of SO2 requires only 5 moles of O2 for the
complete reaction. So here SO2 is the limiting reagent and 5 moles of O2 remains unreacted.

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Q3) A reaction mixture for the production of NH3 gas contains 250 g of N2 gas and 50
g of H2 gas under suitable conditions. Identify the limiting reactant if any and
calculate the mass of NH3 gas produced.
Ans: Nitrogen reacts with Hydrogen to form ammonia according to the equation,
N2(g) + 3H2(g) 2NH3(g)
28g 6g 34g
28g N2 requires 6g H2 for the complete reaction.
So, 250g N2 requires, 6x 250/28 = 53.57g H2.
But here there is only 50g H2.
So we have to consider the reverse case.
i.e. 6g H2 requires 28g N2.
So, 50g H2 requires 28 x 50/6 = 233.33g N2
Here H2 is completely consumed. So it is the limiting reagent.
Amount of ammonia formed = 50+ 233.33 = 283.33 g
Reactions in solutions
Solutions are homogeneous mixture containing 2 or more components. The component which is present
in larger quantity is called solvent and the other components are called solutes. Or, the substance which
is dissolved is called solute and the substance in which solute is dissolved is called solvent.
For e.g. in NaCl solution, NaCl is the solute and water is the solvent.
A solution containing only 2 components are called binary solution. If the solvent is water, it is
called aqueous solution.
The composition of a solution is expressed in terms of concentration. It is defined as the amount of
solute present in a given volume of solution. Concentration can be expressed in the following ways:
1. Mass percent (w/w or m/m): It is defined as the number of parts solute present in 100
parts by mass of solution.
Mass of solute × 100
i.e. Mass % of a component =
Mass of solution
2. Mole fraction: It is defined as the ratio of the number of moles of a particular
component to the total number of moles of solution.
Number of moles of the component
i.e. Mole fraction of a component =
Total number of moles of all the components
For example, in a binary solution, if the number of moles of A and B are n A and nB respectively,
nA
then mole fraction of the component A (χA ) =
nA + nB
nB
and mole fraction of the component B (χB ) =
nA + nB
nA nB
χA + χB = + =1
nA + nB nA + nB
i.e. the sum of the mole fractions of all the components in a solution is always equal to 1.
If there are 1,2,3, …….. i components, then χ1 + χ2 + χ3 + ………………………. + χi = 1
3. Molarity (M): It is the number of moles of solute dissolved per litre of solution.
Number of moles of solute (n)
i.e. Molarity (M) =
Volume of solution in litre (V)
1 M NaOH solution means 1 mole (40 g) of NaOH is present in 1 L of solution.

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When a solution is diluted from one concentration to another, its new concentration can be
calculated by the equation: M1V1 = M2V2.
Where M1 - initial molarity, M2 - final molarity, V1 - initial volume and V2 - final volume.
4. Molality (m): It is defined as the number of moles of solute present per kilogram (kg)
of the solvent.
Number of moles of solute
i.e. Molality (m) =
Mass of solvent in kg
Among the concentration terms, molarity depends on temperature because it is related to
volume, which changes with temperature. All the others are temperature independent.
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
Q4) Calculate the molarity of a solution containing 8 g of NaOH in 500 mL of
water.
Ans: Here mass of solute (NaOH) = 8 g and volume of solution = 500 mL = 0.5 L
Molar mass of NaOH = 40 g mol-1
mass of NaOH in gram 8
No. of moles of NaOH = = 40 = 0.2 mol
Molar mass of NaOH
Number of moles of solute (n) 0.2
Molarity = = = 0.4 M
Volume of solution in litre (V) 0.5

Q5) Calculate the mass of oxalic acid dihydrate (H2C2O4.2H2O) required to

prepare 0.1M, 250 ml of its aqueous solution.
Ans: Here molarity of solution = 0.1M and volume of solution = 250 mL = 0.25 L
No. of moles of oxalic acid = Molarity x volume of solution in litre = 0.1 x 0.25 = 0.025 mol
Molar mass of Oxalic acid dihydrate = 126 g/mol
Mass of oxalic acid = No. of moles x Molar mass of oxalic acid = 0.025 x 126 = 3.15 g
Q6) Calculate the amount of CO2(g) produced by the reaction of 32g of CH4 (g)
and 32g of O2 (g).
Ans: CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)
16g 64g 44g 36g
64g O2 requires 16g CH4 for the complete reaction.
So, 32g O2 requires 8g CH4.
16g CH4 combines with 64g O2 to form 44g CO2.
Therefore, 8g CH4 combines with 32g Oxygen to form 22g CO2
Q7) If the density of methanol is 0.793 kg L–1, what is its volume needed for
making 2.5 L of its 0.25 M solution?
Ans: Density of methanol = 0.793 kg L-1
i.e. mass of 1 L of methanol = 0.793 kg = 793 g
𝑀𝑎𝑠𝑠 𝑖𝑛 𝑔𝑟𝑎𝑚 793
No. of moles of methanol (CH3OH) = = = 24.78 mol
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 32
Molarity = no. of moles of solute per L of solution = 24.78 M
Here we have to prepare 2.5L (V2) of 0.25M (M2) methanol solution from 24.78M (M1) methanol.
So we can use the equation M1V1 = M2V2
24.78 x V1 = 0.25 x 2.5 = 0.025 L = 25 mL
Volume of methanol required = 25 mL

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2. STRUCTURE OF ATOM
The word ‘atom’ has been derived from the Greek word ‘a-tomio’ means ‘uncutable’ or ‘non-
divisible’. The first atomic theory of matter was proposed by John Dalton in 1808. Dalton’s atomic theory
was able to explain the law of conservation of mass, law of constant proportion and law of multiple
proportion very successfully. However, it failed to explain many experimental results.
Discovery of Sub-atomic particles
1. Discovery of Electron
Electron was discovered by J J Thomson through Cathode ray discharge tube experiment. A
cathode ray tube is made of glass containing two thin metal pieces (called electrodes) sealed in it. The
electrical discharge through the gases could be observed only at very low pressures and at very high
voltages.

When a very high voltage (about 10,000 volts) is applied between the two electrodes, no electric
discharge occurs at normal pressure. When the pressure of the gas inside the tube is less than 1 mm of
mercury, a dark space appears near the cathode. When the pressure is reduced to 0.01 mm Hg, it fills
the whole tube. When the pressure is further reduced (10-4 mm Hg), the electric discharge passes
between the electrodes and the tube begins to glow. This is due to the striking of some invisible rays
from the cathode. These rays which start from the cathode and move away from it, in
straight lines are called cathode rays or cathode ray particles.
These rays can be further checked by making a hole in the anode and coating the tube behind
anode with phosphorescent material like zinc sulphide. When these rays strike the zinc sulphide coating,
a bright spot on the coating is developed.
Properties of Cathode Rays
i. The cathode rays start from cathode and move towards the anode.
ii. They are invisible, but their behaviour can be observed with the help of fluorescent
or phosphorescent materials.
iii. In the absence of electrical or magnetic field, these rays travel in straight lines.
iv. In the presence of electric or magnetic field, the cathode rays behave similar to that
of negatively charged particles. From this, it is clear that the cathode rays consist of
negatively charged particles called electrons.
v. The characteristics of cathode rays (electrons) do not depend upon the material of
electrodes and the nature of the gas present in the cathode ray tube.
vi. These rays possess kinetic energy and hence can do mechanical work.
vii. They can produce x-rays when incident on metals with high atomic mass.
Charge to Mass (e/me) Ratio of Electron
J.J. Thomson measured the ratio of electrical charge (e) to the mass of electron (m e ) by using
cathode ray tube and applying electrical and magnetic field perpendicular to each other as well as to the

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path of electrons. There is a fluorescent screen on one side of the discharge tube. When these rays
strike the fluorescent screen, a bright spot is developed.

In the absence of electric or magnetic field, the cathode rays hit the screen at point B. When only
electric field is applied, the electrons deviate from their path and hit the cathode ray tube at point A.
Similarly, when only magnetic field is applied, electron strikes the cathode ray tube at point C. By
carefully balancing the electrical and magnetic field strength, it is possible to bring back the electron
beam to the point B. From the strength of electric and magnetic field, Thomson was able to calculate the
value of e/me as:
e/me = 1.758 × 1011 C kg–1
Where, me is the mass of the electron in kg and e is the magnitude of the charge on the electron in
coulomb (C).
Charge on the Electron (e)
R.A. Millikan determined the charge on the electrons by a method known as ‘oil drop
experiment’. He found that the charge on the electron to be – 1.6022 × 10–19 C.
Mass of electron (me)
The mass of the electron (me) was determined as follows:
Mass of electron (me) = e = 1.6022 x 10-19
e/me 1.758 x 1011
= 9.1 ×10–31 kg
2. Discovery of Protons
E. Goldstein modified the discharge tube experiment by perforated (with small holes) cathode.
After evacuating the tube and on applying high voltage, he found that some rays were emitting behind
the cathode and moving in the opposite direction of cathode rays. These rays deflect to the negative
plate of electric field. So they carry positive charge and were called anode rays or canal rays.

Anode rays Cathode rays

Properties of Canal rays

The characteristics of canal rays are:
i. They depend on the nature of gas present in the cathode ray tube. These are
positively charged gaseous ions.
ii. The charge to mass ratio of anode rays depends on the nature of the gas.
iii. Some of the positively charged particles carry a multiple of the fundamental unit of
electric charge.
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iv. They also travel in straight lines in the absence of electrical or magnetic field.
v. The behaviour of these particles in the magnetic or electrical field is opposite to that
observed for cathode rays.
vi. They can produce heating effect and can do mechanical work.
vii. They are invisible and can be observed with the help of fluorescent or phosphorescent
materials.
The smallest and lightest positive ion was obtained from hydrogen and was called proton.
3. Discovery of Neutrons
Neutrons were discovered by James Chadwick by bombarding a thin sheet of beryllium by α-
particles.
9 4
4Be + 2He → 126C + 10n
They are electrically neutral particles having mass slightly greater than that of the protons.
Characteristics of sub-atomic particles
Sub atomic Symbol Discoverer Absolute Charge Relative Mass (in kg)
particle (in Coulomb) charge
Electron E J J Thomson -1.6022 x 10-19 -1 9.01x10-31
Proton P E Goldstein +1.6022x10-19 +1 1.6726x10-27
Neutron N James Chadwick 0 0 1.675x10-27
Some important terms relating to Atomic structure
Atomic Number: It is the number of protons present in the nucleus or number of electrons present
outside the nucleus.
It is denoted by the symbol ‘Z’.
Atomic number (Z) = nuclear charge or number of protons (p)
= number of electrons (e)
Mass Number: It is the total number of protons and neutrons in atom. Or, it is the total number of
nucleons in an atom.
It is denoted by ‘A’.
i.e. Mass number (A) = no. of protons (p) + no. of neutrons (n)
or, A = p + n
By knowing the atomic number and mass number, we can calculate the number of neutrons as: n = A – Z
If an element X has the atomic number Z and the mass number A, it is denoted as: A𝑧X or ZXA
Isotopes, Isobars and Isotones
Isotopes are atoms with same atomic number but different mass number. That is, they contain
same number of protons but different number of neutrons.
Hydrogen has three isotopes: Protium ( 11H), Deuterium ( 21H or 21D) and Tritium ( 31H or 31T). Among
these, Protium is the ordinary hydrogen and Tritium is the radioactive isotope of Hydrogen.
The number of protons, neutrons and electrons present in the 3 types of hydrogen are:
Isotope Number of protons Number of electrons Number of neutrons
Protium 1 1 0
Deuterium 1 1 1
Tritium 1 1 2
Almost all the elements have isotopes. All the isotopes of a given element have same chemical
properties, but they differ in their physical properties.

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Isobars are atoms of different elements having same mass number but different atomic number.
i.e. they have different number of protons but have equal sum of the protons and neutrons (nucleons).
40 40
e.g. 146C and 147N 18Ar and 20Ca
Isotones are atoms having same number of neutrons but have different atomic numbers. Some
examples are:
Isotones p e N
14
6C 6 6 8
15 7 7 8
7N
16
8O 8 8 8
ATOM MODELS
1. Thomson’s Model of Atom
J. J. Thomson proposed the first atom model, which is known as the plum pudding or raisin
pudding or watermelon model.
According to this model:
• an atom has a spherical shape in which the positive charge is uniformly distributed.
• The electrons are distributed in it, just like the seeds are distributed in a water melon or
plums are distributed in a pudding.
• The mass of the atom is uniformly distributed over the atom.
• The total positive charge in an atom is equal to the total negative charge and hence the
atom is electrically neutral.
This model was able to explain the electrical neutrality of the atom. But it failed to explain the
experimental observations made by Rutherford and others.
2. Rutherford’s Nuclear Model of Atom
Earnest Rutherford proposed an atom model based on α–particle scattering experiment. He
bombarded a very thin gold foil [approximately 10-7m or 100 nm thickness] with α–particles.
The Experiment: A stream of high energy α–particles from a radioactive source was directed at a thin
gold foil. The thin gold foil had a circular fluorescent zinc sulphide screen (photographic plate) around it.
Whenever α–particles struck the screen, a tiny flash of light was produced at that point.

[Rutherford’s scattering experiment] [Schematic molecular view of the gold foil]

Observations and conclusions of α–particle scattering experiment are:
Observations Conclusions
1. Most of the α– particles passed 1. Most space in the atom is empty.
through the gold foil without any
deviation.
2. A small fraction of the α– 2. The positive charge of the atom is
particles was deflected by small concentrated in a very small volume at the
angles. centre called nucleus.

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3. A very few α– particles 3. The volume occupied by the nucleus is

(approximately 1 out of 20,000) negligibly small as compared to the total
bounced back [i.e. deflected by volume of the atom. [The radius of the atom
nearly 180°]. is about 10–10 m, while that of the nucleus is
10–15 m].

On the basis of above observations and conclusions, Rutherford proposed the nuclear model of atom or
Planetary model of atom. According to this model:
1. The positive charge and most of the mass of the atom are concentrated in an
extremely small region called nucleus.
2. Electrons are revolving round the nucleus with a very high speed in circular paths
called orbits.
3. Electrons and the nucleus are held together by electrostatic forces of attraction.

Drawbacks or Limitations of Rutherford’s atom model

1. Rutherford’s model could not explain the stability of the atom.
2. It could not explain the electronic structure of atom.

Wave nature of Electromagnetic Radiation

James Clerk Maxwell suggested that when electrically charged particle moves under
acceleration, alternating electrical and magnetic fields are produced and transmitted. These fields are
transmitted in the forms of waves called electromagnetic waves or electromagnetic radiation (emr).
These are the radiations associated with electrical and magnetic fields.
The important characteristics of these radiations are:
1. The oscillating electrical and magnetic fields are perpendicular to each other and both are
perpendicular to the direction of propagation of the wave.
2. The electromagnetic waves do not require a medium for propagation and can move in vacuum.
3. There are many types of electromagnetic radiations, which differ from one another in
wavelength (or frequency). These constitute electromagnetic spectrum. The important
electromagnetic radiations in the increasing order of wavelength are:
Cosmic rays, Gamma rays, X-rays, Ultra-violet rays, Visible light, Infra-red rays, Microwaves,
Radio waves.
4. All electromagnetic radiations travel with a constant speed of 3x108 m/s through vacuum.
Some important terms relating to electromagnetic radiations
1. Frequency (ν): It is defined as the number of waves that pass through a given point in one
second. The SI unit for frequency is hertz (Hz) or s–1.
2. Wavelength (λ) : It is the distance between two adjacent crusts or troughs. Its unit is m or cm.
Commonly the wavelength of electromagnetic radiations are expressed in nanometer (nm) or
Angstrom unit (A0). 1nm = 10-9 m = 10-7 cm 1A0 = 10-10 m = 10-8 cm.
3. Speed of light (c): It is the distance travelled by an electromagnetic radiation in one second.
c = 3x108 m/s in vacuum.
The frequency (ν), speed of light (c) and the wave length (λ) are related to each other as: c = ν λ
𝒄
Or, ν = 𝛌
4. Wave number (ῡ): It is defined as the number of wavelengths per unit length. Or, it is the
reciprocal of wavelength. i.e. ῡ = 1/ λ. Its SI unit is m–1. But it is commonly expressed in cm-1.
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Particle Nature of Electromagnetic Radiation: Planck’s Quantum Theory

Some of the experimental phenomenon like diffraction and interference can be explained by the
wave nature of the electromagnetic radiation. But some phenomena like black body radiation,
photoelectric effect, variation of heat capacity of solids with temperature, line spectra of atoms etc.
could not be explained by the wave nature of electromagnetic radiation.
Black body radiation
An ideal body which emits and absorbs all frequencies of radiations is called a black
body and the radiation emitted by such a body is called black body radiation.
A perfect black body is rare. But carbon black behaves nearly like a black body.
The amount of light emitted (intensity of radiation) from a black body and its spectral distribution
depends only on its temperature. At a given temperature, intensity of radiation emitted increases with
the increase of wavelength, reaches a maximum value and then decreases.
The phenomenon of black body radiation was first explained by Max Planck by his Quantum
theory. According to this theory:
1. Atoms and molecules could emit (or absorb) energy not in a continuous manner, but
discontinuously in small packets of energy called quanta or photons.
2. The energy (E) of a quantum of radiation is proportional to its frequency (ν). i.e. E = hν.
Where ‘h’ is known as Planck’s constant (h = 6.626×10–34 Js).
Photoelectric effect
It is the phenomenon of ejection of electrons by certain metals (like potassium,
rubidium, caesium etc.) when light of suitable frequency incident on them. The electrons
ejected are called photoelectrons.
This phenomenon was first observed by Heinrich Hertz.
The important results observed in photoelectric effect are:
1. The electrons are ejected from the metal surface as soon as the beam of light
strikes the surface. i.e., there is no time lag between the striking of light beam and
the ejection of electrons from the metal surface.
2. The number of electrons ejected is proportional to the intensity or brightness of
light.
3. For each metal, there is a minimum frequency (known as threshold frequency [ν0])
below which photoelectric effect is not observed.
4. The kinetic energy of the ejected electrons is directly proportional to the
frequency of the incident light.
Explanation of photoelectric effect by Einstein
A satisfactory explanation to photoelectric effect was first given by Albert
Einstein using Planck’s quantum theory.
According to him, when a photon of sufficient energy strikes the metal surface, it suddenly transfers
its energy to the electron of the metal atom and the electron is ejected without any time lag. A part of
this energy is used to eject the electron from the metal surface (i.e. to overcome the attractive force of
the nucleus). This energy is called work function [hν0]. The other part of this energy is given to the
ejected electron in the form of kinetic energy. Greater the energy possessed by the photon, greater will
be transfer of energy to the electron and greater the kinetic energy of the ejected electron.
Since the striking photon has energy equal to hν and the minimum energy required to eject the
electron is hν0 (also called work function, W0) then the difference in energy (hν – hν0) is transferred as

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the kinetic energy of the photoelectron.

Applying the law of conservation of energy principle, the kinetic energy of the ejected electron is given
by K.E = hν - hν0
Or, hν = hν0 + ½ mev2
Where me is the mass of the electron and v is the velocity of the ejected electron.
A more intense beam of light contains larger number of photons, so the number of electrons
ejected is also larger.
Q1) The threshold frequency for a metal is 7.0 x 1014 s-1. Calculate the kinetic
energy of an emitted electron when radiation of frequency (ν) 1.0 x 1015 s-1 hits
the metal.
Ans: Here threshold frequency (ν0) = 7.0 x 1014 s-1 and frequency of radiation (ν) = 1.0 x 1015 s-1

K.E of emitted electron = hν - hν0 = h(ν - ν0) = 6.626 x 10-34 (1.0 x 1015 - 7.0 x 1014) = 19.878 x 10-20 J

Dual Behaviour of Electromagnetic Radiation

Some phenomena of electromagnetic radiations can be explained by the wave nature of emr,
but some others can be explained by its particle nature. So electromagnetic radiations possess both
particle and wave nature. This is known as dual nature of Electromagnetic Radiation. When radiation
interacts with matter, it shows particle like nature.
Atomic spectrum
When a ray of white light is passed through a prism, we get a series of coloured bands called
spectrum. This spectrum is called continuous spectrum, because here violet merges into blue, blue into
green and so on.
Similarly, when electromagnetic radiation interacts with matter, atoms and molecules may
absorb energy and reach to a higher energy unstable state. To attain stability, they emit radiations in the
form of spectrum. Such a spectrum is called atomic spectrum.
Emission and Absorption Spectra
The spectrum of radiation emitted by a substance that has absorbed energy is
called an emission spectrum. Atoms, molecules or ions that have absorbed radiation are said to be
“excited”. To produce an emission spectrum, energy is supplied to a sample by heating it or irradiating it
and the wavelength (or frequency) of the radiation emitted is recorded.
An absorption spectrum is like the photographic negative of an emission spectrum.
Here a continuum of radiation (like white light) is passed through a sample which absorbs
radiation of certain wavelengths. The missing wavelengths leave dark spaces in the bright
continuous spectrum.
The study of emission or absorption spectra is referred to as spectroscopy.
The emission spectra of atoms in the gas phase do not form a continuous spectrum. The excited
atoms emit light only at specific wavelengths with dark spaces between them. Such spectra are called
line spectra or atomic spectra.
Line emission spectra are very useful in the study of electronic structure of atoms. Each element
has a unique line emission spectrum. The characteristic lines in atomic spectra can be used in chemical
analysis to identify unknown atoms in the same way as finger prints are used to identify people. So line
emission spectra are also called finger print of atoms.
Line Spectrum of Hydrogen
When an electric discharge is passed through gaseous hydrogen, the H2 molecules dissociate and
the energetically excited hydrogen atoms produced emit electromagnetic radiation of discrete

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frequencies. The hydrogen spectrum consists of several series of lines named after their discoverers. The
first five series of lines are Lyman, Balmer, Paschen, Brackett and Pfund series. Among these lines,
the Balmer series is the only series that we can be visible (since it lies in the visible region of
emr).
Johannes Rydberg proposed an equation for finding the wave number of the different lines in
𝟏 𝟏 𝟏
Hydrogen spectrum. The expression is: Ѷ = 𝝀 = 𝟏𝟎𝟗𝟔𝟕𝟕 {𝒏𝟐 − } cm-1
𝟏 𝒏𝟐𝟐
Where n1 = 1, 2, 3,….. and n2 = n1 + 1, n1 + 2, ……
The different spectral lines, their spectral region and their n1 and n2 values are as follows:
Series Spectral region n1 n2
Lyman series Ultra violet 1 2,3,4….
Balmer series Visible 2 3,4,5….
Paschen series Infra-red 3 4,5,6…..
Brackett series Infra-red 4 5,6,7….
Pfund series Infra-red 5 6,7,8…..

3. BOHR’S MODEL FOR HYDROGEN ATOM

The general features of the structure of hydrogen atom and its spectrum were first explained by
Niels Bohr. The important postulates of his theory are:
1. The electron in the hydrogen atom can move around the nucleus in circular paths of
fixed radius and energy. These paths are called orbits or stationary states or allowed
energy states. These energy levels are numbered as 1,2,3 etc or as K, L, M, N, etc. These numbers
are known as Principal quantum numbers.
2. The energy of an electron in an orbit does not change with time. However, when an
electron absorbs energy, it will move away from the nucleus (i.e. to a higher energy level) and
when it loses energy, it will move towards the nucleus (i.e. to a lower energy level).
3. The radius of orbits can be given by the equation: rn = a0 n2 where a0 = 52.9 pm.
Thus the radius of the first stationary state is 52.9 pm (called the Bohr radius). As n increases, the
value of r will increase.
1
4. The energy of electron in an orbit is given by the expression: En = -RH. 𝑛2 , where n =
1,2,3…… and RH is a constant called Rydberg constant. Its value is 2.18x10-18 J. The energy
of the lowest state (the ground state) is given by E1 = –2.18×10–18J. As the value of n increases,
the energy of the electron also increases.
5. The frequency of radiation absorbed or emitted when transition occurs between two
∆E E2 − E1
stationary states that differ in energy by ΔE, is given by: ν = =
h h
Where E1 and E2 are the energies of lower and higher energy levels respectively. This expression is
commonly known as Bohr’s frequency rule.
6. The angular momentum of an electron is quantized. i.e. it is an integer multiple of
h/2π.
𝑛ℎ
Or, Angular momentum, mevr =
2π
Where me is the mass of electron, v is the velocity of electron and r is the radius of Bohr orbit. n =
1,2,3..... Thus an electron can move only in those orbits whose angular momentum is an integral
multiple of h/2π. So only certain fixed orbits are allowed.

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Significance of negative energy of electron

When the electron is free from the influence of nucleus, its energy is taken as zero. In this
situation, the electron is at the orbit with n = ∞. When the electron is attracted by the nucleus and is
present in orbit n, the energy is emitted and its energy is lowered. That is the reason for the presence of
negative sign in equation.
Explanation of Line Spectrum of Hydrogen
According to Bohr atom model, radiation is absorbed if the electron moves from lower energy to
higher energy level and radiation is emitted if the electron moves from higher orbit to lower orbit. The
energy gap between the two orbits is given by equation:
ΔE = E2 – E1
R R
But E1 = nH2 and E2 = nH2
1 2

1 1
Therefore, ΔE = RH [ − ]
𝑛12 𝑛22
1 1
= 2.18 x 10-18 [ − ]
𝑛12 𝑛22

The frequency associated with the absorption and emission of the photon can be given as:
∆𝐸 𝑅𝐻 1 1
ν= = [ − ] Hz
ℎ ℎ 𝑛12 𝑛22
2.18 x 10−18 J 1 1
= [ − ] Hz
6.626 x 10−34 Js n21 n22
1 1
= 3.29 𝑥 1015 [n2 − n22
] Hz
1

1 ν RH 1 1
The wave number (Ѷ) = = = [ − ] m-1
𝛌 c hc n21 n22

3.29 x 1015 1 1
= [ − ] m-1
3 x 108 n21 n22
1 1
= 1.09677 𝑥 107 x [ − ] m-1
n21 n22
1 1
= 109677 x [ − ] cm-1
n21 n22

In case of absorption spectrum, n2 > n1 and the term in the bracket is positive and energy is
absorbed. On the other hand, in case of emission spectrum n1 > n2, ΔE is negative and energy is
released.
Limitations of Bohr Atom Model:
Bohr atom model could explain the stability and line spectra of hydrogen atom and hydrogen like ions
(e.g. He+, Li2+, Be3+ etc). But it has the following limitations:
1. It could not explain the fine spectrum of hydrogen atom.
2. It could not explain the spectrum of atoms other than hydrogen.
3. It was unable to explain the splitting of spectral lines in the presence of electric field
(Stark effect) and in magnetic field (Zeeman effect).
4. It could not explain the ability of atoms to form molecules by chemical bonds.
5. It did not consider the wave character of matter and Heisenberg’s uncertainty principle.

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Dual Behaviour of Matter – de Broglie’s equation

de Broglie proposed that like radiation, matter also exhibit dual behaviour i.e., both particle and
wave like properties. This means that electrons should also have momentum as well as wavelength. He
gave the following relation between wavelength (λ) and momentum (p) of a material particle.
h h
λ= =
p mv
Where m is the mass of the particle, v is the velocity and p is the momentum. The above
equation is known as de Broglie’s equation.
Like electromagnetic radiations, an electron beam also undergoes diffraction. This is an evidence for
the wave nature of electrons. An electron microscope works on the principle of wave nature of electron.
According to de Broglie, every moving object has a wave character. The wavelengths associated
with ordinary objects are so short (because of their large masses) that their wave properties cannot be
detected. The wavelengths associated with electrons and other subatomic particles (with very small
mass) can be detected experimentally.
Heisenberg’s Uncertainty Principle
Werner Heisenberg proposed the uncertainty principle which is the consequence of dual behaviour of
matter and radiation. It states that “it is impossible to determine simultaneously, the exact
position and exact momentum (or velocity) of a moving microscopic particle like electron”.
Mathematically, it can be given as in equation:
h
Δx. Δp ≥
4π
h
Or, Δx. mΔv ≥
4π
h
Or, Δx. Δv ≥
4πm
Where Δx is the uncertainty in position and Δp (or, Δv) is the uncertainty in momentum (or
velocity) of the particle.
If the position of the electron is known with high degree of accuracy (Δx is small), then the velocity of
the electron will be uncertain [Δv is large] and vice versa.
Significance of Uncertainty Principle
Heisenberg Uncertainty Principle is significant only for motion of microscopic objects and is not
applicable to macroscopic objects. According to this Principle, we cannot determine the exact position
and momentum of an electron. Thus it rules out the existence of definite paths or orbits of electrons.
We can only say the probability of finding an electron at a given point.
Reasons for the Failure of the Bohr Model
In Bohr model, electrons are moving in well-defined circular orbits about the nucleus. The wave
character of the electron is not considered in Bohr model. Further, an orbit is a clearly defined path and
this path can completely be defined only if both the position and the velocity of the electron are known
exactly at the same time. This is not possible according to the Heisenberg uncertainty principle.
Therefore, Bohr model of the hydrogen atom not only ignores dual behaviour of matter but also
contradicts Heisenberg uncertainty principle.
QUANTUM MECHANICAL MODEL OF ATOM
On the basis of dual nature of matter and the uncertainty principle, Erwin Schrodinger and
Werner Heisenberg proposed a new model of atom called Quantum mechanics. The fundamental
equation of quantum mechanics was developed by Schrödinger and is known as Schrödinger equation. It
is written as: Ĥ ψ = Eψ
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where Ĥ is a mathematical operator called Hamiltonian operator, E is the total energy of the system (K.E
+ P.E) and ψ is called the wave function. On solving the above equation, we get different values for E
and ψ.
When Schrödinger equation is solved for hydrogen atom, the solution gives the possible energy
levels the electron can occupy and the corresponding wave function (ψ). These quantized energy states
and corresponding wave functions are characterized by a set of three quantum numbers.
Significance of ψ
The wave function (ψ) is a mathematical function and it has no physical meaning. Wave functions
of hydrogen or hydrogen like species with one electron are called atomic orbitals. All the information
about the electron in an atom is stored in its orbital wave function ψ. It may be positive or negative.
But ψ2 has some physical significance. It gives the probability of finding an electron at a point
within an atom. So ψ2 is known as probability density and is always positive. From the value of ψ2, it is
possible to predict the probability of finding the electron around the nucleus.
Quantum Numbers
These are certain numbers used to explain the size, shape and orientation of orbitals.
Or, Quantum numbers are the address of an electron. There are four quantum numbers
which describe the electron in an atom. They are Principal Quantum number (n), Azimuthal
Quantum number (Ɩ), Magnetic Quantum number (m or mƖ) and Spin Quantum number (s).
1. Principal Quantum Number (n)
The following information are obtained from n.
1. It gives the size of the orbit.
2. It gives the energy of electron in an orbit.
3. It gives the shell in which the electron is found.
4. It also gives the average distance between the electron and the nucleus. As the value
of n increases, the distance between the electron and the nucleus also increases.
The possible values of n are 1, 2, 3, 4, 5 etc.
If n = 1 the electron is in K shell
n = 2 the electron is in L shell
n = 3 the electron is in M shell and so on.
2. Azimuthal Quantum Number [Subsidiary or orbital angular momentum Quantum number] (Ɩ)
The following information are obtained from Ɩ .
1. It gives the shape of the orbital.
2. It gives the sub shell or sub level in which the electron is located.
3. It also gives the orbital angular momentum of the electron.
For a given value of n, Ɩ can have n values ranging from 0 to n – 1. That is, for a given value of n, the
possible value of Ɩ are : Ɩ = 0, 1, 2, .......... (n-1).
For example, when n = 1, value of Ɩ is only 0. For n = 2, the possible value of Ɩ can be 0 and 1. For
n = 3, the possible Ɩ values are 0,1 and 2.
Ɩ= 0 represents s orbital, Ɩ = 1 represents p orbital, Ɩ = 2 represents d orbital and Ɩ = 3 represents f
orbital
The number of sub shells in a principal shell is equal to the value of n. For example,
When n = 1, Ɩ= 0. i.e. K shell contains only one sub shell - s sub shell
when n = 2, Ɩ = 0 and1. i.e. L shell contains two sub shells - s and p sub shells
when n = 3, Ɩ = 0, 1 and 2. i.e. M shell contains three sub shells – s, p and d sub shells
when n = 4, Ɩ = 0, 1, 2 and 3. i.e. N shell contains four sub shells – s, p,d and f sub shells

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3. Magnetic Quantum Number (m or mƖ)

It gives information about the orientation of orbitals in space. For a given ‘Ɩ’ value,
there are (2Ɩ+1) possible values for m and these values are given by : m = – Ɩ to 0 to + Ɩ
Thus for Ɩ = 0, mƖ = 0 [2 x 0+1 = 1]. i.e. s sub shell contains only one orbital called s orbital.
For Ɩ = 1, mƖ = –1, 0 and +1 [2x1+1 = 3]. i.e. p subshell contains three orbitals called p orbitals (px, py and
pz).
For Ɩ = 2, mƖ = –2, –1, 0, +1 and +2 [2x2+1 = 5]. i.e. d subshell contains five orbitals called d orbitals (dxy,
dxz, dyz, dx2- y2 and dz2)
4. Spin Quantum Number (s or ms)
It is the only experimental quantum number and it gives the spin orientation of
electrons. This spin may be either clockwise or anticlockwise. So the values for s may be
+½ or -½. +½ represents clock-wise spin and-½ represents anticlock-wise spin.

Shapes of orbitals
1. s-orbitals
For s-orbitals, Ɩ = 0 and hence mƖ = 0. So there is only one possible orientation for s orbitals. They
are spherically symmetrical. The plots of probability density (ψ2) against distance from the nucleus
(r) for 1s and 2s atomic orbitals are as follows:

For 1s orbital the probability density is maximum at the nucleus and it decreases with increase in
r. But for 2s orbital the probability density first decreases sharply to zero and again starts increasing.
After reaching a small maximum it decreases again and approaches zero as the value of r increases. The
region where the probability density (ψ2) reduces to zero is called nodal surface or node.
For 1s orbital, there is no node, for 2s orbital there is only one node, for 3s orbital
there are 2 nodes and so on. In general, for an ns-orbital there are (n – 1) nodes.
All the s-orbitals are spherically symmetrical and their size increases with increase in n. The
boundary surface diagrams for 1s, 2sand 3s orbitals are as follows:

2. p-orbitals
For p-orbitals, Ɩ = 1 and mƖ = -1, 0, +1. i.e., there are three possible orientations for p orbitals. So
there are 3 types of p-orbitals – px, py and pz. Each p orbital consists of two lobes. The probability density
function is zero on the plane where the two lobes touch each other.

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The size, shape and energy of the three orbitals are identical. They differ only in the orientation of
the lobes. For px orbital, the lobes are along the x-axis, for py, they are along the y-axis and for pz, they
are along the z-axis. All the p-orbitals have dumb-bell shape.
The number of radial nodes for p-orbitals are given by (n –2), that is number of radial
node is 1 for 3p orbital, two for 4p orbital and so on. Besides the radial nodes, the probability
density functions for the np orbitals are zero at the plane, passing through the nucleus (origin). For
example, in the case of pz orbital, xy-plane is a nodal plane. These are called angular nodes and number
of angular nodes is given by ‘Ɩ’.
Number of radial nodes = n - Ɩ – 1
Number of angular nodes = Ɩ
Total number of nodes = n-1
The boundary surface diagrams for three 2p orbitals are as follows:

3. d-orbitals
For d-orbitals, Ɩ = 2 and mƖ = -2, -1, 0, +1 and +2. i.e., there are five possible orientations for d
orbitals. So there are 5 types of d-orbitals. They are dxy, dxz, dyz, dx2- y2 and dz2.
The shapes of the first four d-orbitals are double dumb-bell and that of the fifth one,
2
dz , is dumb-bell having a circular collar in the xy-plane. The five d-orbitals have equivalent
energies. For d-orbitals the number of radial nodes is 2 and the total number of nodes is n-2. Boundary
surface diagrams for d-orbitals are as follows:

4. f-orbitals
For f-orbitals, Ɩ = 3 and mƖ = -3, -2, -1, 0, +1, +2 and +3. i.e., there are seven possible orientations
for f orbitals. So there are 7 types of f-orbitals.
They are fx3, fy3, fz3, fx(y2-z2), fy(z2-x2), fz(x2-y2) and fxyz. They have diffused shapes.

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Rules for Filling of electrons in various orbitals

The filling of electrons into the orbitals of different atoms takes place according to the 3 rules -
aufbau principle, Pauli’s exclusion principle and the Hund’s rule of maximum multiplicity.
1. Aufbau principle:
The German word aufbau means ‘build up’. The building up of orbitals means the filling up of
orbitals with electrons.
The principle states that the orbitals are filled in the increasing order of their
energies. In other words, electrons first occupy the lowest energy orbital and then to
higher energy orbitals.
This rule has two sub rules:
a) The various orbitals are filled in the increasing order of their (n+Ɩ) value.
b) If two orbitals have the same (n+Ɩ) values, the orbital with the lower n value is filled first.
The increasing order of orbitals is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s...
2. Pauli’s Exclusion Principle
It states that no two electrons in an atom can have the same set of four quantum
numbers. i.e. an orbital can accommodate a maximum of only 2 electrons with opposite spin.
If 2 electrons have same values for n, Ɩ and m, they should have different values for s. i.e. if s =
+½ for the first electron, it should be -½ for the second electron.
3. Hund’s rule of maximum multiplicity
It states that electron pairing takes place only after partially filling all the
degenerate orbitals. [Orbitals having same energies are called degenerate orbitals]. For example the
electronic configuration of N is 1s2 2s2 2px1py1pz1 and not 1s2 2s2 2px2py1.

Electronic Configuration of Atoms

The distribution of electrons into various orbitals of an atom is called its electronic configuration.
The electronic configuration of different atoms can be represented in two ways.
(i) sa pb dc ...... notation
(ii) Orbital diagram
The electrons in the completely filled shells are known as core electrons and the electrons in the
outer most shell are called valence electrons.
Stability of Completely Filled and Half Filled Subshells
Atoms having half filled or completely filled electronic configurations have extra
stability compared to other atoms. This is due to their symmetrical distribution of
electrons and greater exchange energy.
For example, the electronic configuration of Cr is [Ar] 3d54s1 and not 3d44s2. This is
because d5 represents a half filled configuration and has extra stability. Similarly for Cu,
the electronic configuration is [Ar] 3d104s1 and not 3d94s2. This is due to the greater
stability of completely filled d10 configuration.

**********************************************************************************

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3. CLASSIFICATION OF ELEMENTS AND

PERIODICITY IN PROPERTIES
Earlier classifications
1) Dobereiner’s classification:
Johann Dobereiner classified elements into small groups each containing three elements. These
small groups were called triads.
E.g. for triads are: i) 7Li 23Na 39K

ii) 40Ca 88Sr 137Ba

In triads, the atomic mass of the middle element is approximately the average of the other two
elements. This is known as Law of Triads. This classification was rejected, since the law of triad is
applicable only to a very few elements.
2) Newlands classification:
Newland arranged elements in the increasing order of their atomic masses. He noted that the
properties of every eighth element, starting from a given element, are similar to that of the first
element. The relationship is just like the resemblance of first and eighth musical notes. He named this as
law of octaves.
But his classification was rejected since the law of octaves was applicable to elements upto calcium.
A.E.B. de Chancourtois arranged elements in increasing order of atomic weights and made a
cylindrical table of elements to display the regular repetition of properties.
3) Lothar Meyer’s classification: Lothar Meyer plotted the physical properties of elements like
atomic volume, melting point and boiling point against atomic weight and obtained a periodically
repeated pattern. Based on this, he developed a periodic table similar to that of Mendeleev’s.
4) Mendeleev’s classification:
Dmitri Mendeleev (a Russian chemist) classified the elements in the increasing order of their atomic
weights. He found that the properties of elements repeat after a regular interval. Based on this
observation, he proposed a periodic law which states that “The properties of elements are the
periodic functions of their atomic weights.” That is, when elements are arranged in the increasing
order of their atomic weights, their properties repeat after a regular interval.
Mendeleev’s periodic table contains horizontal rows called series (periods) and vertical
columns called groups. Elements with similar properties are placed in the same group. He
mainly depends on the similarities in the empirical formulae and the properties of the
compounds formed by the elements. So he did not strictly obey the increasing order of
atomic weights. Also he corrected the wrong atomic masses of some elements.
When Mendeleev proposed his periodic table, some of the elements were not discovered. He
left some vacant places (gaps) for them in the periodic table and predicted some of their properties.
For e.g. both Gallium and Germanium were not discovered at that time. He named these elements as
Eka-Aluminium and Eka-Silicon respectively and predicted their properties. These elements were
discovered later and found that Mendeleev’s predictions were correct.
Merits of Mendeleev’s periodic table
1) It was the first comprehensive classification of elements.
2) He corrected the wrong atomic weights of some elements and placed them in correct
position in the periodic table.
3) He left vacant places for undiscovered elements and predicted some of their properties.
4) Elements with similar properties are placed in the same group.

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Demerits of Mendeleev’s periodic table

1) Elements with dissimilar properties are found in same group.
2) He could not give an exact position for hydrogen.
3) He could not give exact position for Lanthanoids and Actinoids and also for isotopes.
4) Mendeleev’s periodic table did not strictly obey the increasing order of atomic weights.
Modern Periodic table
Henry Moseley’s work on the X-ray spectra of elements proved that atomic number is a more
fundamental property than atomic mass. Based on this observation, he modified the Mendeleev’s
periodic law as “the physical and chemical properties of elements are the periodic functions
of their atomic numbers”. This is known as Modern Periodic law.
Based on the modern periodic law, numerous forms of periodic tables have been proposed. The
most commonly used is the long form of periodic table.
In this periodic table, the elements are arranged in the increasing order of their atomic number.
It contains 7 horizontal rows called periods and 18 vertical columns called groups or families.
In the long form of modern periodic table, hydrogen has given a particular position at the top centre.
PERIODS
There are 7 periods in Modern periodic table. The period number corresponds to the highest
principal quantum number of the elements.
Period No. Elements No. of Elements Subshells filled Description
I 1H & 2He 2 1s Very short period
II 3 Li to 10Ne 8 2s & 2p
Short periods
III 11 Na to 18Ar 8 3s & 3p
IV 19K to 36Kr 18 4s, 3d & 4p
Long periods
V 37Rb to 54Xe 18 5s, 4d & 5p
VI 55Cs to 86Rn 32 6s, 4f, 5d & 6p
Longest periods
VII 87 Fr to 118 Og 32 7s, 5f, 6d & 7p
The 14 elements each of sixth and seventh periods are placed in separate rows below the main
body of the periodic table. These are together called inner transition elements. The 14 elements of
sixth period [from 57Ce (cerium) to 71Lu (lutetium)] are called Lanthanides or Lanthanones or
Lanthanoids or rare earths. The 14 elements of seventh period [from 90Th (thorium) to 103Lr
(lawrencium)] are called Actinides or Actinones or Actinoids.
GROUPS
Vertical columns in Long form of Modern periodic table are called groups or families. There are
18 groups and these are numbered from 1 to 18. Due to the similar outer electronic configuration and
same valency, the elements present in the same group have similar properties.
Group General outer
Elements Family name
No. Electronic configuration
1 Li, Na, K, Rb, Cs & Fr ns1 Alkali metals
2 Be, Mg, Ca, Sr , Ba & Ra ns2 Alkaline earth metals
3 to 12 4 rows of elements (n-1)d1 to 10 ns 0 to 2 Transition elements
13 B, Al, Ga, In, Tl & Nh ns2 np1 Boron Family
14 C, Si, Ge, Sn, Pb & Fl ns2 np2 Carbon Family
15 N, P, As, Sb, Bi & Mc ns2 np3 Nitrogen Family
16 O, S, Se, Te, Po & Lv ns2 np4 Oxygen Family
17 F, Cl, Br, I, At, Ts ns2 np5 Halogen Family
18 He, Ne, Ar, Kr, Xe, Rn, Og ns2 np6 Noble gases

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The Blocks in the Modern periodic table

The Modern periodic table is divided into 4 blocks based on the subshell in which
the last electron enters. They are s block, p block, d block and f block.
1. The s-block elements
These are elements in which the last electron enters in the outer most s sub shell.
They include elements of the groups 1 and 2. Their general outer electronic configuration
is ns1 or ns2. They are all reactive metals with low ionization enthalpies. They lose their
outer most electrons readily to form +1 and +2 ions. Their metallic character and
reactivity increases down the group. They mainly form ionic compounds (except Li and Be).
2. The p-block elements
These are elements in which the last electron enters in the outer most p sub shell.
They include elements of the groups 13 to 18. Their general outer electronic configuration
is ns2 np1 to 6. Their non-metallic character increases from left to right in a period and
metallic character increases from top to bottom in a group.
The 18th group elements are called Noble gases or inert gases. They have completely filled orbitals
and so they do not undergo chemical reactions at ordinary conditions.
s and p block elements are together called Representative elements, because these are the only
elements which show the general trends in the periodic table and also they contain metals, non-metals
and metalloids.
3. The d-block elements
These are elements in which the last electron enters in the penultimate d sub shell. They
include elements of the groups 3 to 12. They are also called Transition elements (Transition
metals), since they show a regular transition (change) from the most electropositive s block
elements to the least electropositive p block elements. Their general outer electronic
configuration is (n-1)d1 to 10 ns0 to 2.
Some properties of transition elements are:
a) They are all metals.
b) They form coloured compounds or ions in aqueous solution.
c) They show variable oxidation states and valencies.
d) They are generally paramagnetic.
e) They show catalytic properties.
4. The f-block elements
These are elements in which the last electron enters in the anti-penultimate f sub
shell. They include lanthanides of 6th period and actinides of 7th period. They are also
called Inner transition elements. Their general outer electronic configuration is (n-2)f1 to
14
(n-1)d0 to 1 ns2. They are all metals. Within each series the properties of these elements
are similar. Actinoid elements are radioactive. Elements after Uranium (z=92) in the actinide
series are called trans-uranium elements or trans-uranic elements or artificial elements. [Neptunium
(93Np) and Plutonium (94Pu) are also found naturally in Pitch blende, an ore of Uranium].
Electronic configuration of an element and its position in the periodic table
From the electronic configuration of an element, we can assign its period, group and block in the
periodic table.

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Block: The subshell in which the last electron enters.

Period number = the highest principal quantum number in its electronic configuration.
Group number: For s-block elements = no. of valence s electrons
For p-block elements = no. of valence s electrons + valence p electrons + 10
For d-block elements = no. of valence s electrons + no. of penultimate d electrons.

Nomenclature of elements with atomic numbers > 100

For naming elements with atomic number > 100, IUPAC has made some recommendations. A
systematic nomenclature be derived directly from the atomic number of the element using the
numerical roots for 0 and numbers 1-9.
Digit 0 1 2 3 4 5 6 7 8 9
Root name nil un bi tri quad pent hex sept oct enn
Abbreviation n u b t q p h s o e
The roots are put together in order of digits which make up the atomic number and “ium” is added at
the end.
Atomic Number Name according to Symbol IUPAC Official Name
IUPAC nomenclature and Symbol
101 Unnilunium Unu Mendelevium (Md)
102 Unnilbium Unb Nobelium (No)
103 Unniltrium Unt Lawrencium (Lr)
104 Unnilquadium Unq Rutherfordium (Rf)
105 Unnilpentium Unp Dubnium (Db)
106 Unnilhexium Unh Seaborgium (Sg)
107 Unnilseptium Uns Bohrium (Bh)
108 Unniloctium Uno Hassium (Hs)
109 Unnilennium Une Meitnerium (Mt)
110 Ununnilium Uun Darmstadtium (Ds)
111 Unununium Uuu Rontgenium (Rg)
112 Ununbium Uub Copernicium (Cp)
113 Ununtrium Uut Nihonium (Nh)
114 Ununquadium Uuq Flerovium (Fl)
115 Ununpentium Uup Moscovium (Mc)
116 Ununhexium Uuh Livermorium (Lv)
117 Ununseptium Uus Tennessine (Ts)
118 Ununoctium Uuo Oganesson (Og)
119 Ununennium Uue
120 Unbinilium Ubn

Periodic properties of Elements

The properties which repeat after a regular interval are called periodic properties. Some of the
important periodic properties of elements are atomic and ionic radii, ionization enthalpy, electron gain
enthalpy, electropositivity, electronegativity etc.

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1. Atomic Radius
It is defined as the distance from the centre of the nucleus to the outermost shell having
electrons. Atomic radius of individual atoms cannot be determined. So it is expressed in any of the
following methods:
a) Covalent radius: It is half of the inter nuclear distance between two covalently bonded (single
bonded) atoms. It is used to express the atomic radius of non-metal atoms. For e.g. the bond
distance of Cl2 molecule is 198 pm. So the covalent radius is 99 pm.
b) Metallic radius: It is the half of the inter nuclear distance between two metallic ions in a metal
crystal.
c) van der Waal’s radius: It is defined as the half of the inter nuclear distance between two non-
bonded atoms of separate molecules in the solid state.
Atomic radius is commonly expressed in picometre (pm) or angstrom (A0) unit. [1 pm = 10-12m and
1 A = 10-10 m]. It is measured by x-ray diffraction method or by spectroscopic method.
0

Variation of atomic radius along a group and a period

The atomic size decreases from left to right in a period. This is because in a period,
the electrons are added to the same valence shell. Thus the number of shells remains
same, but the effective nuclear charge increases. So the atomic radius decreases. In a given
period, alkali metals (group 1) have the maximum size and halogens (group 17) have the minimum size.
In a group, the atomic radius increases from top to bottom. This is because of the
increase in no. of shells and shielding effect. (In atoms with higher atomic number, the inner
electrons partially shield the attractive force of the nucleus. So the outer electrons do not experience
the full attraction of the nucleus and this is known as shielding effect or screening effect).
Atomic radius of noble gases is larger than that of halogens. This is because noble
gases are monoatomic. So van der Waal’s radius is used to express the atomic radius which
is greater than covalent radius or metallic radius.
2. Ionic radius
It is defined as the half of the inter nuclear distance between cations and anions of an ionic crystal.
The variation of ionic radius is same as that of atomic radius.
Generally a cation is smaller than its parent atom (e.g. Na+ is smaller than Na atom).
This is because a cation has fewer electrons, but its nuclear charge remains the same as
that of the parent atom.
An anion is larger than its parent atom (e.g. Cl- is larger than Cl atom). This is because
the addition of one or more electrons would result in an increased electronic repulsion and
a decrease in effective nuclear charge.
Isoelectronic species:
Atoms and ions having the same number of electrons are called isoelectronic
species. E.g. O2-, F-, Ne, Na+, Mg2+ etc. (All these contain 10 electrons)
Among isoelectronic species, the cation with greater positive charge will have the smaller radius.
This is because of the greater attraction of electrons to the nucleus. The anion with greater negative
charge will have the larger radius. Here the repulsion between electrons is greater than the attraction of
the nucleus. So the ion will expand in size.
3. Ionisation enthalpy (∆iH)
It is defined as the energy required to remove an electron from the outer most shell
of an isolated gaseous atom in its ground state. It may be represented as:
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X(g) + ∆iH → X+(g) + e–

Its unit is kJ/mol or J/mol.
The energy required to remove the first electron from the outer most shell of a neutral atom is called
first ionisation enthalpy (∆iH1).
X(g) + ∆iH1 → X+(g) + e–
Second Ionisation enthalpy (∆iH2) is the amount of energy required to remove an electron from a
unipositive ion.
X+(g) + ∆iH2 → X2+(g) + e–
Energy is always required to remove an electron from an atom or an ion. So ∆iH is always positive.
The second ionisation enthalpy is always higher than first ionization enthalpy. This is
because it is more difficult to remove an electron from a positive charged ion than from a
neutral atom.
Similarly third ionisation enthalpy is higher than second ionisation enthalpy and so on.
i.e. ∆iH1 < ∆iH2 < ∆iH3…………
As the ease of removal of electron increases, the ionisation enthalpy decreases.
Factors affecting ionisation enthalpy
The important factors which affect ionisation enthalpy are:
a) Atomic size: Greater the atomic size (atomic radius), smaller will be the ionisation enthalpy.
b) Nuclear charge: The value of ionisation enthalpy increases with nuclear charge.
c) Shielding effect: As the shielding effect increases, the electrons can easily be removed and so the
ionisation enthalpy decreases.
d) Presence of half-filled or completely filled orbitals increases ionisation enthalpy.
Variation of ∆iH along a period and a group
Along a period, ionisation enthalpy increases from left to right. This is because of
the decrease in atomic radius and increase in nuclear charge. Thus alkali metals have the
least ∆iH and noble gases have the most.
Down a group, ∆iH decreases due to increase in atomic radius and shielding effect.
Thus among alkali metals, lithium has the highest ∆iH and francium has the lowest.
In the second period of modern periodic table, the first ionisation enthalpy of Boron
is slightly less than that of Beryllium. This is because after the removal of one electron
from boron, it gets the stable configuration (1s22s2). So B loses one electron faster.
Similarly the first ionisation enthalpy of nitrogen is greater than that of oxygen.
This is because N has half filled electronic configuration (1s22s22p3), which is more stable
and so more energy is required to remove an electron.
4. Electron gain enthalpy (∆egH)
It is the heat change (enthalpy change) when an electron is added to the outer most
shell of an isolated gaseous atom. It can be represented as X(g) + e– → X-(g)
Its unit is kJ/mol. It may be positive or negative depending on the nature of the element. For
most of the elements, energy is released when electron is added to their atoms. So ∆ egH is negative.
Noble gases have large positive electron gain enthalpy because of their completely
filled (stable) electronic configuration.
Electron gain enthalpy also depends on atomic size, nuclear charge, shielding effect etc. As the
atomic size increases, ∆egH becomes less negative. When nuclear charge increases, electron gain

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enthalpy becomes more negative. As shielding effect increases, ∆egH becomes less negative. Presence of
half-filled or completely filled orbitals make ∆egH less negative.
Periodic variation of ∆egH
From left to right across a period, ∆egH become more negative. This is because of decrease in
atomic radius and increase in nuclear charge. So the ease of addition of electron increases.
Down a group, ∆egH becomes less negative. This is due to increase in atomic radius and shielding effect.
Electron gain enthalpy of fluorine is less negative than chlorine. This is because,
when an electron is added to F, it enters into the smaller 2nd shell. Due to the smaller size,
the electron suffers more repulsion from the other electrons. But for Cl, the incoming
electron goes to the larger 3rd shell. So the electronic repulsion is low and hence Cl adds
electron more easily than F. [OR, Due to the compactness of the 2p subshell of F, electronic
repulsion is greater in F and hence it does not easily add electron]. Due to the same reason ∆egH of
oxygen is less negative than sulphur.
Thus in modern periodic table, alkali metals have the least negative ∆egH and halogens have the
most negative ∆egH. Among halogens, ∆egH becomes less negative in the order: Cl> F > Br > I
[The negative electron gain enthalpy is also called electron affinity].
5. Electronegativity
Electronegativity of an atom in a compound is the ability of the atom to attract
shared pair of electron of electrons. It is not a measurable quantity and so it has no unit. There are
different scales for measuring the Electronegativity of elements. The most commonly used is the Pauling
Electronegativity scale developed by Linus Pauling.
Electronegativity depends on atomic size and nuclear charge. As the atomic radius increases,
electronegativity decreases. Greater the nuclear charge, greater will be the electronegativity. Generally
electronegativity increases across a period and decreases along a group. So in modern periodic table,
Fluorine is the most electronegative element and Francium is the least electronegative element. Since
francium is radioactive, caesium is the least electronegative stable element. In Pauling Scale,
electronegativity of Fluorine is 4.0 and that of Oxygen is 3.5.
The electronegativity of an element is not constant. It varies depending on the element to which it is
bound. It is directly related to the non-metallic character of elements. An increase in electronegativity
across a period indicates an increase in non-metallic character and decrease in metallic character.
6. Electropositivity
It is the tendency of an atom to lose the most loosely bound electron (valence
electron). It is directly related to the metallic character of elements. It depends on atomic size and
nuclear charge. As the atomic radius increases, electropositivity increases.
Along a period, electropositivity decreases from left to right. But down a group, it increases. So
francium is the most electropositive element and fluorine is the least electropositive element.
7. Valency
It is the combining capacity of an element. Or, it is the number of electrons lost or
gained by an atom during a chemical reaction.
Along a period, valency first increases upto the middle and then decreases (for s and p block
elements only). In a group, valency remains constant. Transition elements can show variable valency.
Valency is numerically equal to oxidation number of the element. The difference is that oxidation
number has a positive or negative sign but the valency doesn’t.

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Anomalous Properties of Second Period Elements

The first element in groups 1 (lithium) and 2 (beryllium) and groups 13 to 17 (boron
to fluorine) differs from the other members of their respective group in their properties.
This is known as anomalous properties. This is due to their small size, large charge to
radius ratio, high electronegativity and absence of vacant d-orbitals.
Some of the anomalous properties are:
• They can form multiple bonds with themselves (e.g. C = C, N ≡ N etc.) and with
other elements of the second period (e.g. C = O, C ≡ N etc.).
• Their maximum co-valency is 4, due to the absence of vacant d-orbitals. But other
elements of the respective groups can expand their covalency beyond 4 (due to the
presence of vacant d-orbitals). For this reason, Aluminium forms [AlF6]3- whereas boron
cannot form [BF6]3- but forms only [BF4]- . Similarly, Phosphorus forms PCl5 while nitrogen
cannot form NCl5.
Diagonal relationship
The similarities in properties shown by the diagonally placed elements of the 2nd and
3rd periods in the Modern periodic table are called Diagonal relationship. This is due to
their similar atomic radii, ionisation enthalpy, electronegativity etc.
E.g. Lithium shows similarities with Mg, Be with Al, B with Si etc.

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4. CHEMICAL BONDING AND MOLECULAR STRUCTURE

The attractive force that binds the atoms together in a molecule is called a
chemical bond. It is formed either by the transfer of electrons or by the sharing of electrons.
Lewis symbols
In the formation of a chemical bond, only the outermost electrons participate and these
electrons are called valence electrons. The inner electrons are well protected and they are called core
electrons.
G.N Lewis introduced simple notations to represent valence electrons in an atom. These
notations are called Lewis symbols or Lewis notations. Here the nucleus and the inner electrons are
represented by the symbol of the element and the valence electrons by dots or crosses.
E.g. for sodium [11Na -2,8,1], the Lewis symbol is and for chlorine [17Cl -2,8,7] is
Lewis symbols are informative. It gives the valency of an atom, which is either equal to the
number of dots or crosses or equal to 8 – no. of dots or crosses.
Octet rule
This rule was proposed by Lewis and Kossel. According to this rule, atoms undergo
chemical reaction in order to attain an octet of electrons in the valence shell. Or, atoms
containing 8 electrons in their valence shell are stable.
Ionic or Electrovalent Bond
A bond formed by the transfer of electron between 2 atoms is called ionic or electrovalent bond.
Or, it is the force of attraction between two oppositely charged ions.
E.g. formation of NaCl
11Na + 17Cl → Na+Cl-
2,8,1 2,8,7
In Na atom, there is only one electron in the valence shell and in Cl, there are 8 electrons in the valence
shell. In order to attain octet state, Na atom loses one electron and form Na + ion and Cl atom gains one
electron and form Cl- ion. These two ions attract each other by electrostatic force called ionic bond.
Na → Na+ +e-
2,8,1 2,8
Cl + e-→ Cl-
2,8,7 2,8,8
Na+ + Cl-→ NaCl
Energy changes during the formation of an ionic bond
An ionic bond formation involves the following steps:
1) The formation of a positive ion (cation) from the electropositive atom. The amount
of energy required for this process is called ionisation enthalpy (∆iH).
M(g) + ∆iH → M+(g) + e-
2) Formation of negative ion from the electronegative atom. The energy involved in this
process is called electron gain enthalpy (∆egH).
X(g) + e- → X-(g) + ∆egH
3) The packing of the cation and anion to form an ionic compound. The energy change in
this process is called lattice enthalpy (∆latticeH)
M+ + X- → MX(s) + ∆latticeH
So the factors favouring the ionic bond formation are:
i) Low ionisation enthalpy of the electropositive atom (metal atom)

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ii) High negative electron gain enthalpy of the electronegative atom (non-metal atom)
iii) High lattice enthalpy of the ionic compound formed.
Lattice Enthalpy
It is the energy required to completely separate one mole of an ionic compound into
corresponding gaseous ions. Or, it is the energy released when one mole of an ionic compound is
formed from gaseous ions.
The stability of an ionic compound is determined by its Lattice Enthalpy. Generally greater the
Lattice Enthalpy, stabler will be the compound.
Covalent bond
A bond formed by the mutual sharing of electrons between two or more atoms is
called covalent bond.
e.g. 1) The formation of Chlorine molecule (Cl2)
17Cl + 17Cl → Cl2
2,8,7 2,8,7
Both the chlorine atoms have 7 electrons in their outermost shell. So here the exchange of
electrons is not possible. For the formation of Cl2 molecule, each Cl atom shares one pair of electron.
The bond thus formed is called a single covalent bond.

2) The formation of O2 molecule

8O + 8O → O2
2,6 2,6
To attain octet, each oxygen atom shares 2 pairs of electrons. Thus a double covalent bond is formed.

or
3) The formation of N2 molecule
7N + 7N → N2
(2,5) (2,5)
To attain the octet configuration, the nitrogen atoms share 3 pairs of electrons. Thus a triple
bond is formed.

In the formation of a covalent bond, each combining atoms contribute at least one electron to
the shared pair. The number of electrons contributed by an atom to the shared pair (bonded pair)
during the formation of a covalent bond is called covalency. In the formation of Cl2 molecule, the
covalency of each Cl atoms is one, in O2 molecule, the covalency of O atom is 2 and in N2, it is 3.
The double and triple bonds are together called multiple bonds. A covalent bond formed by the
sharing of one pair of electron is called a single bond. A double bond is formed when 2 pairs of electrons
are shared between 2 atoms and a triple bond is formed when 3 pairs of electrons are shared between
two atoms.
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Limitations of Octet rule

1) It could not explain the stability of compounds with incomplete octet (containing less than 8
electrons around the central atom). E.g. LiCl, BeH2, BCl3 etc.
2) It could not explain the stability of molecules containing odd number of electrons like NO,
NO2 etc.
3) It could not explain the stability of molecules containing more than 8 electrons around the
central atom (i.e. expanded octet). E.g. PF5, SF6, H2SO4, IF7 etc.
4) octet rule is based upon the chemical inertness of noble gases. But some noble gases like
xenon and krypton form compounds with F and O.
5) This theory does not account for the shape of molecules.
6) It does not explain the relative stability of the molecules.
Bond Parameters
1) Bond Length: It is defined as the average equilibrium distance between the nuclei of two bonded
atoms in a molecule. It is measured by spectroscopic, X-ray diffraction and electron diffraction
techniques. It is expressed in pico-metre (pm) or in angstrom unit (A0).
2) Bond Angle: It is defined as the angle between the orbitals containing bonding electron pairs
around the central atom in a molecule. It can be experimentally determined by spectroscopic
methods. It is expressed in degree.
3) Bond Enthalpy: It is defined as the amount of energy required to break one mole of a particular
bond between 2 atoms in gaseous state. Its unit is kJ/mol.
For diatomic molecules, bond enthalpy is equal to bond dissociation enthalpy. Larger the bond
dissociation enthalpy, stronger will be the bond formed. For poly atomic molecules, the bond
enthalpy is the average of the bond dissociation enthalpies.
4) Bond order: It is defined as the number of bonds between 2 atoms in a molecule. For H 2, bond
order = 1, for O2, bond order = 2 and for N2, bond order = 3. Isoelectronic molecules and ions
have identical bond orders.
Generally with increase in bond order, bond enthalpy increases and bond length decreases.
Resonance Structures
In the case of some compounds, all the observed properties cannot be explained by a single
structure. Here we use more than one structures of the compound. These different structures are
called resonance structures or canonical structures or contributing structures. The phenomenon is
known as resonance. Resonating structures are separated by double headed arrows.
e.g. i) Ozone (O3)

The actual structure of ozone is not I or II. It is a resonance hybrid of the structures I and II which
can be represented as structure III.

ii) Carbon dioxide (CO2)

iii) Benzene (C6H6)

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Characteristics of resonance
a) Resonance stabilizes the molecule. As the number of resonating structures increases, the
stability also increases.
b) Resonance changes the bond length.
c) The difference in energy between the actual structure and the most stable canonical
structure is called resonance energy. Greater the resonance energy, stabler will be the
molecule.
Polarity of bonds – Dipole moment
When a covalent bond is formed between 2 similar atoms, the shared pair of electrons is equally
attracted by the two atoms. So the electron pair is exactly between the two nuclei. The bond so formed
is called a non-polar covalent bond.
But when the covalent bond is formed between 2 dissimilar atoms, the shared electron pairs are
more attracted by one of the atoms. So one atom gets a slight negative charge (δ-) and the other gets a
slight positive charge (δ+). Such molecules are called polar molecules. E.g. HCl, HF, H2O, HI etc.
The polarity of a molecule is expressed in terms of dipole moment (μ). It is defined as the
product of the magnitude of charge at one end (Q) and distance between the charges (r).
Mathematically, μ = Q x r.
The unit of dipole moment is Coulomb metre (Cm). But it is usually expressed in the unit Debye (D).
1D = 3.336 x 10-30 Cm.
Dipole moment is a vector quantity. i.e. it has both magnitude and direction. It is denoted by a small
arrow with tail on the positive centre and head pointing towards the negative centre.
e.g.: HF
In the case of poly atomic molecules, dipole moment depends on the individual bond dipoles and
the spatial arrangement of bonds. Here the dipole moment of the molecule is the vector sum of the
bond dipoles of various bonds.
e.g. H2O

For BeF2, the net dipole moment is zero, since the two equal bond dipoles are in
opposite directions and cancel each other.

In BF3, the net dipole moment is zero. Here the resultant of any 2 bond dipoles is equal
and opposite to the third.

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Both ammonia (NH3) and nitrogen fluoride (NF3) are pyramidal in shape. Even though
F is more electro negative than H, the net dipole moment of NF3 is smaller than that of
NH3. This is because in the case of NH3, the orbital dipole due to lone pair is in the same
direction as the resultant dipole moment of the three N – H bonds. But in NF3, the orbital
dipole is in the opposite direction to the resultant dipole moment of the three N-F bonds.
So the dipole moments get partially cancelled.

NH3 (μ = 1.47D) NF3 (μ = 0.23D)

Covalent character in ionic bonds – Fajans Rules

The partial covalent character of ionic bonds was explained by Fajans in terms of the following rules:
1) The smaller the size of the cation and the larger the size of the anion, the greater
the covalent character of an ionic bond.
2) The greater the charge on the cation, the greater the covalent character of the
ionic bond.
3) For cations of the same size and charge, the ion with electronic configuration
(n-1)dnns0 is more polarising than the ion with a noble gas configuration (ns2 np6).
THE SHAPES OF MOLECULES
Covalent bonds are directional in nature. i.e. they are directed to some specified positions in
space. So covalent compounds have definite shapes.
The Valence Shell Electron Pair Repulsion [VSEPR] Theory
This theory was proposed by Sidgwick and Powell and later modified by Nyholm and Gillespie.
The important postulates of this theory are:
1) The shape of the molecule depends on the number of valence shell electron pairs
(VSEPRs) around the central atom.
2) The valence shell electron pairs repel each other.
3) In order to reduce the repulsion, the electron pairs stay at maximum distance.
4) The valence shell is taken as a sphere with the electron pairs localising on the
spherical surface at maximum distance from one another.
5) A multiple bond is treated as if it is a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
6) If a molecule has resonance structures, the VSEPR model is applicable to any such
structure.
7) Presence of lone pairs of electron causes distortion in the expected geometry of
the molecule.
8) The repulsion between two lone pairs of electrons is different from those between
two bond pairs or between a lone pair and bond pair. The repulsion decreases in the
order lone pair - lone pair > lone pair - bond pair > bond pair - bond pair.
9) As the angle between the electron pairs increases, the repulsion decreases.
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Prediction of geometry of molecules using VSEPR theory

I) Molecules containing only bond pairs of electrons:
1) AB2 type (where A is the central atom and B is the no. of bond pairs)
Here there are 2 VSEPs. In order to reduce the repulsion, these electron pairs are arranged at an
angle of 1800. Thus the shape of the molecule is linear with bond angle 180 0.
E.g. BeCl2, HgCl2 etc.

2) AB3 type
Here there are 3 VSEPs. In order to reduce the repulsion, these electron pairs are arranged at an
angle of 1200. Thus the shape of the molecule is planar triangular (trigonal planar) with bond angle 120 0.
e.g. BF3, BCl3 etc.

3) AB4 type
Here there are 4 VSEPs. These are arranged at the four corners of a tetrahedron and hence the shape
of the molecule is tetrahedral with bond angle 109028l. e.g.: CH4, NH4+ etc.

4) AB5 type
Here there are 5 VSEPs. To reduce the repulsion, they are arranged at the five corners of a trigonal
bipyramid with bond angles 1200 and 900. E.g. PCl5

5) AB6 type
Here there are 6 VSEPs. To reduce the repulsion, they are arranged at the six corners of an
octahedron with bond angles 900. E.g.: SF6

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II) Molecules containing both bond pairs and lone pairs:

The presence of lone pairs of electron causes distortion in the shape of the molecules.

Type of Total no. No. of No. of Shape E.g.

molecule of VSEPs b.ps l.ps
AB2E 3 2 1 Bent SO2, O3
Trigonal Pyramid NH3
AB3E 4 3 1

AB2E2 4 2 2 Bent H2O

AB4E 5 4 1 See-saw SF4

AB3E2 5 3 2 T-Shape ClF3

AB5E 6 5 1 Square Pyramid BrF5

AB4E2 6 4 2 Square Planar XeF4

Explanation of shapes of ammonia and water molecules by VSEPR theory

1. NH3
In ammonia, the central atom N has 5 valence electrons (7N – 2,5). Among these electrons, three
are used for the formation of bonds with hydrogen atoms and the remaining 2 electrons stay as lone
pairs. So there are 4 VSEPs. Hence the expected shape of the molecule is tetrahedral. But due to the
presence of lone pairs, the shape is distorted to triangular pyramid and the bond angle changes from
109028l to 1070.

2. H2O
In water, the central atom O has 6 valence electrons (8O – 2,6). Two of them are used for the
formation of bonds with hydrogen atoms and the remaining 4 electrons stay as lone pairs. So there are 4
VSEPs. Hence the expected shape of the molecule is tetrahedral. But due to the presence of 2 lone pairs,
the shape is distorted to bent or angular or inverted v shape and the bond angle changes from 109028l
to 104.50.

Orbital overlap concept

Orbital overlapping is the process of partial interpenetration of atomic orbitals. The important
characteristics of orbital overlapping are:
1. A covalent bond is formed by the overlapping of half-filled atomic orbitals present in the valence
shell of atoms.
2. The overlapping orbitals should contain electron with opposite spin.
3. As a result of overlapping, the electrons get paired and a stable covalent bond is formed.
4. The strength of a covalent bond depends on the extent of overlapping. The greater the extent of
overlapping, the stronger will be the covalent bond formed.

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Types of overlapping
There are two types of orbital overlapping.
1. Axial overlapping:
If the overlapping of atomic orbitals take place along inter nuclear axis, it is called
axial overlapping or end to end overlapping. A bond formed by axial overlapping is called
sigma (σ) bond. The electrons present in sigma bond are called sigma electrons. All single bonds are
sigma bonds. A sigma bond can be formed by the following ways:
i) s-s overlapping: Here the overlapping of two half-filled s-orbitals take place along the inter
nuclear axis.

ii) s-p overlapping: It occurs with the overlapping of one half filled s-orbital and one half filled p-
orbital.

iii) p-p overlapping: Here two half-filled p- orbitals of two atoms overlap.

2. Lateral overlapping:
Here the overlapping take place perpendicular to the inter nuclear axis. The bond
formed as a result of lateral overlapping is called pi (π) bond. The electrons in pi bond are
called π electrons.

A π bond is always present along with σ bonds. A double bond contains one σ bond and one π
bond. A triple bond contains one sigma bond and two pi bonds.
A sigma bond is stronger than a pi bond. This is because the extent of overlapping is greater in a
sigma bond.
Hybridisation
It is the process of inter mixing atomic orbitals having slightly different energies
to form new orbitals having equivalent energy and identical shape. The new orbitals formed
are called hybrid orbitals.
Characteristics of hybridisation
1. The number of hybrid orbitals formed is equal to the number of atomic orbitals
undergo hybridization.
2. The hybrid orbitals are always equivalent in energy and in identical shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.
4. The hybrid orbitals are directed to some fixed positions in space. So the type of
hybridization gives the shape of the molecule.

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Important conditions of hybridisation

a) The orbitals present in the valence shell of the atom are hybridized.
b) The orbitals undergoing hybridization should have almost equal energy.
c) Promotion of electrons is not an essential condition before hybridisation.
d) Completely filled orbitals of valence shell can also take part in hybridisation.
Types of hybridisation
1. sp3 hybridisation: It is the process of inter mixing of one s-orbital and three p-
orbitals to form four new orbitals having equivalent energy and shape. The 4 new orbitals
formed are called sp3 hybrid orbitals. They are directed to the four corners of a regular
tetrahedron with bond angle 109028l. Each sp3 hybrid orbitals has 25% s-character and 75% p-
character.
E.g. i) Formation of methane (CH4)
In CH4, the central atom C has the electronic configuration
2 2 2
6C – 1s 2s 2p

C (ground state) –
In order to explain the tetra valency of C, it is suggested that one of the electrons of 2s orbital is
promoted to 2p orbital.

C (excited state) –
Now, one s-orbital and three p-orbitals undergo sp3 hybridisation. These sp3 hybrid orbitals are directed
to the four corners of a regular tetrahedron with bond angle 109 028l. Each of these sp3 hybrid orbitals
overlap with 1s orbital of H to form four C-H σ bonds.

ii) Formation of ethane (C2H6)

In ethane, each C atom undergoes sp3 hybridisation. Out of the 4 sp3 hybrid orbitals, one of each C
atom overlaps axially to form a C-C σ bond. The remaining 3 sp3 hybrid orbitals of each C atom overlap
with 1s orbital of H atom to form 6 C-H σ bonds.

iii) Formation of Ammonia (NH3) molecule

In NH3, the central atom N has the electronic configuration 1s22s22p3.

The one s-orbital and three p-orbitals of N undergo sp3 hybridisation to form 4 sp3 hybrid orbitals. One
of this sp3 hybrid orbitals is occupied by a lone pair and the other three sp 3 hybrid orbitals overlap with
1s orbital of hydrogen to form 3 N-H bonds. Due to the greater repulsion between lone pair and bond
pairs, the shape is distorted to pyramidal and the bond angle becomes 1070.
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iv) Formation of water (H2O) molecule

In H2O, the central atom O has the electronic configuration 1s22s22p4.

Now the one s-orbital and three p-orbitals of O undergo sp3 hybridisation to form 4 sp3 hybrid
orbitals. Two of these sp3 hybrid orbitals are occupied by lone pairs and the other two sp3 hybrid orbitals
overlap with 1s orbital of hydrogen to form 2 O-H bonds. Due to the greater repulsion between lone
pairs, the shape is distorted to angular shape or bent structure or inverted ‘v’ shape and the bond angle
becomes 104.50.

2. sp2 hybridisation: It is the process of inter mixing of one s-orbital and two p-orbitals to
form three new orbitals having equivalent energy and shape. The 3 new orbitals formed are
called sp2 hybrid orbitals. They are directed to the three corners of an equilateral
triangle. So the shape of the molecule is planar triangular or trigonal planar with bond
angle 1200. Each sp2 hybrid orbitals has 33% s-character and 66% p-character.
E.g. i) Formation of BCl3
Here the central atom B has the electronic configuration 1s22s22p1. In the excited state, one of the 2s
electrons is promoted to vacant 2p orbital. So the configuration becomes 2s12p2.
Now one s-orbital and two p-orbitals undergo hybridisation. The 3 hybrid orbitals formed overlap with
2p orbitals of Cl to form 3 B-Cl σ bonds. Since the hybridisation is sp2, the shape of the molecule is planar
triangular with bond angle 1200.

ii) Formation of ethane or ethylene (C2H4)

In ethane, each C atom undergoes sp2 hybridisation. Out of the 3 sp2 hybrid orbitals, one of each
C overlaps axially to form a C-C σ bond. The remaining two sp2 hybrid orbitals of each C
overlap with the 1s orbital of H to form 4 C-H σ bonds.
Now each C atom has one unhybridized p-orbital, which overlaps laterally to form a π bond. Thus
there are 5 σ bonds and one π bond in ethane.

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3. sp hybridisation: It is the process of inter mixing of one s-orbital and one p-

orbital to form two new orbitals having equivalent energy and shape. The 2 new orbitals
formed are called sp hybrid orbitals. They are directed in a line. So the shape is linear
with bond angle 1800. Each sp hybrid orbitals has 50% s-character and 50% p-character.
e.g. i) Formation of BeCl2
in BeCl2, the central atom Be has the electronic configuration 1s22s2. In the excited state, one of the
2s electrons is promoted to 2p level. So the configuration becomes 1s22s12p1.
Now one s-orbital and one p-orbital undergo sp hybridisation to form 2 new sp hybrid orbitals.
Each of these hybrid orbitals overlaps with the 2p orbitals of Cl to form 2 Be-Cl bonds. So the shape of
the molecule is linear with bond angle 1800.

ii) Formation of ethyne or acetylene (C2H2)

In acetylene, each C atom undergoes sp hybridisation. Out of the 2 sp hybrid orbitals, one of the
sp hybridized orbitals of each carbon, overlaps axially to form a C-C σ bond. The remaining one sp hybrid
orbital of each carbon overlap with the 1s orbital of hydrogen atoms to form 2 C-H σ bonds.
Now each C atom has 2 unhybridized p-orbitals, which overlap laterally to form 2 π bonds. Thus
the molecule has linear shape with bond angle 1800. Hence there are 3 σ bonds and 2 π bonds in ethyne.

4. sp3d hybridisation: It is the process of inter mixing of one s-orbital, three p-

orbitals and one d-orbital to form five new orbitals having equivalent energy and shape.
The 5 new orbitals formed are called sp3d hybrid orbitals. These are directed to the five
corners of a regular trigonal bipyramid with bond angles 1200 and 900.
E.g. Formation of PCl5
In PCl5, the central atom P has the electronic configuration 2 3 0
15P – [Ne] 3s 3p 3d
To satisfy the penta valency of P, one of the 3s electrons is promoted to 3d level.

Now, one s-orbital, three p-orbitals and one d-orbital undergo sp3d hybridisation. These 5 sp3d hybrid
orbitals are directed to the five corners of a regular trigonal bipyramid with bond angles 1200 and 900.
In PCl5, three P-Cl bonds lie in one plane, at an angle of 1200. These three bonds are
called equatorial bonds. The other two P-Cl bonds lie one above and one below this plane.
They are called axial bonds. The axial bond pairs suffer more repulsion from the equatorial
bond pairs. So the axial bond length is greater than the equatorial bond length. So PCl5 is
highly unstable and is very reactive.

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5. sp3d2 hybridisation: It is the process of inter mixing of one s-orbital, three p-

orbitals and two d-orbitals to form six new orbitals having equivalent energy and shape.
The 6 new orbitals formed are called sp3d2 hybrid orbitals. These are directed to the six
corners of a regular octahedron with bond angle 900.
e.g. Formation of SF6
In SF6 the central sulphur atom has the ground state outer electronic configuration 3s 23p4. In the
exited state one electron each from 3s and 3p orbitals are promoted to 3d level.

Now one s-orbital, three p-orbitals and two d-orbitals undergo sp3d hybridisation. These hybrid orbitals
overlap with p- orbitals of fluorine atoms to form 6 S–F sigma bonds. Thus SF6 molecule has a regular
octahedral geometry with bond angle 900.

VALENCE BOND THEORY

This theory was introduced by Heitler and London and later developed by Linus Pauling in order
to explain the shape of molecules theoretically. VBT can be explained by considering the formation of H 2
molecule.
Consider 2 hydrogen atoms A and B with nuclei NA and NB and electrons eA and eB respectively.
When the two atoms are at large distance from each other, there is no interaction between them. So
their potential energy is zero. When the two atoms approach each other, new attractive and repulsive
forces begin to operate.
Attractive forces arise between nucleus of one atom and electron of other atom i.e., NA– eB and NB– eA.
Repulsive forces arise between electrons of two atoms, i.e. eA – eB, and the nuclei of two atoms NA – NB.
Attractive forces bring the two atoms close to each other whereas repulsive forces push them away.
Experimentally, it has been found that the magnitude of new attractive force is more than the
new repulsive forces. So the two atoms approach each other and potential energy decreases. At a
particular stage, the net attractive force balances the net repulsive forces and the energy becomes
minimum. At this stage, the hydrogen atoms are saidto be bonded together to form a stable molecule.
The distance between the two atoms at this stage is called bond length (74 pm). The amount of energy
liberated at this stage is called bond enthalpy(435.8kJ/mol)

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The potential energy diagram for the formation of H2 molecule is as shown below:

Molecular Orbital Theory

This theory was developed by F.Hund and R.S Mulliken. The important postulates of this theory are:
1) In molecules, the electrons are present in some special type of orbitals called
molecular orbitals (M.Os).
2) The atomic orbitals (A.Os) of comparable energy and proper symmetry combine to
form molecular orbitals.
3) Atomic orbitals are monocentric, while molecular orbitals are polycentric. i.e.
electrons present in atomic orbitals are attracted by only one nucleus. While the
electrons present in molecular orbitals are attracted by more than one nuclei.
4) The number of molecular orbitals formed = the number of atomic orbitals combined.
i.e. if 2 atomic orbitals combined, 2 molecular orbitals are formed. One is called
bonding molecular orbital (BMO) and the other is called anti-bonding molecular
orbitals (ABMO)
5) The BMO has lower energy and greater stability than the corresponding ABMO.
6) The molecular orbitals give the electron probability distribution around a group of
nuclei.
7) The molecular orbitals are filled according to 3 rules – Aufbau principle, Pauli’s
exclusion principle and Hund’s rule.
Formation of molecular orbitals – Linear Combination of Atomic Orbitals (LCAO) method
Molecular orbitals are formed by the combination of atomic orbitals by an approximate method
known as Linear Combination of Atomic Orbitals (LCAO). According to this theory, the combinations of
atomic orbitals take place by addition and subtraction of wave functions of atomic orbitals. The M.O
formed by the addition of A.Os is called the bonding molecular orbital (BMO) and by the subtraction of
A.Os is called the anti-bonding molecular orbitals (ABMO).
The electron density in a BMO is located between the nuclei of the bonded atoms. So the
repulsion between the nuclei is very low. Therefore a BMO always possess lower energy than the
combining A.Os. While in the case of an ABMO, most of the electron density is located away from the
space between the nuclei. There is a nodal plane between the nuclei and hence the repulsion between
the nuclei is high. So an ABMO possess higher energy than the combining A.Os. ABMO is denoted by
using an asterisk (*) mark.
Conditions for the combination of atomic orbitals
The combination of A.Os to form M.Os takes place only if the following conditions are satisfied:

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1. The combining A.Os must have the same or nearly the same energy.
2. The combining A.Os must have the same symmetry about the molecular axis.
3. The combining A.Os must overlap to the maximum extent.
Types of molecular orbitals
M.Os of diatomic molecules are designated as σ (sigma), π (Pi), δ (delta) etc. the sigma M.Os are
symmetrical about the bond axis, while the pi M.Os are not symmetrical.
Linear combination of two 1s atomic orbitals produces two M.Os – a BMO σ1s and an ABMO σ*1s.
Similarly linear combination of two 2s atomic orbitals produces two M.Os – σ2s and σ*2s.
If z-axis is taken as the inter nuclear axis, linear combination of two 2p z orbitals produces two sigma
M.Os σ2pz and σ*2pz.
While the combination of 2px and 2py orbitals produce M.Os which are not symmetrical about
the bond axis. So two 2px orbitals produces 2 sigma M.Os – π2px and π*2px and two 2py orbitals produce
2 M.Os – π2py and π*2py.
Energies of various M.Os
The various M.Os are filled in the increasing order of their energies (Aufbau Principle).
The increasing order of energy is:
σ1s < σ*1s < σ2s < σ*2s < (π2px = π2py) <σ2pz < (π*2px= π*2py) < σ*2pz
For O2, F2 and Ne2, the order is:
σ1s < σ*1s < σ2s < σ*2s < σ2pz < (π2px = π2py) < (π*2px= π*2py) < σ*2pz
Bond Order
It is defined as the half of the difference between the number of bonding electrons
(Nb) and the number of anti-bonding electrons (Na).
i.e. Bond order (B.O) = ½ [Nb – Na]
A molecule is stable only if the bond order is positive. (i.e. Nb > Na). A negative or zero
bond order (i.e. Nb < Na or Nb = Na) means an unstable molecule.
For a single bond, B.O = 1, for a double bond B.O = 2 and so on. Bond order gives an approximate
measure of the bond length. In general, as the bond order increases, bond length decreases and bond
enthalpy increases.
Molecular orbital configuration and Bond order of some Homonuclear diatomic molecules

Molecule M.O configuration No. of No. of Anti- Bond Order =

Total no.
Bonding bonding ½ [Nb –Na]
of
Electrons electrons
electrons
(Nb) (Na)
H2 σ1s2 2 2 0 = ½ [2 – 0] = ½ x 2 = 1
He2 σ1s2 σ*1s2 4 2 2 = ½ [2 – 2] = ½ x 0 = 0
Li2 σ1s2 σ*1s2 σ2s2 6 4 2 = ½ [4 – 2] = ½ x 2 = 1
Be2 σ1s2 σ*1s2 σ2s2 σ*2s2 8 4 4 = ½ [4 – 4] = ½ x 0 = 0
B2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [6 – 4] = ½ x 2 = 1
10 6 4
π2px1 π2py1
C2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [8 – 4] = ½ x 4 = 2
12 8 4
π2px2 π2py2
N2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 4] = ½ x 6 = 3
14 10 4
π2px2 π2py2 σ2pz2

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O2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 6] = ½ x 4 = 2

σ2pz2 π2px2 π2py2 16 10 6
π*2px1 π*2py1
F2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 8] = ½ x 2 = 1
σ2pz2 π2px2 π2py2 18 10 8
π*2px2 π*2py2
Ne2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 10] = ½ x 0 = 0
σ2pz2 π2px2 π2py2 20 10 10
π*2px2 π*2py2 σ*2pz2

He2, Be2 and Ne2 molecules do not exist, since their Bond orders are zero. H2, Li2, B2 and
F2 molecules contain a single bond, since their bond order = 1, C2 and O2 molecules contain a double
bond, since their B.O = 2 and for N2, there is a triple bond since its bond order = 3.
Magnetic nature
If all the M.Os in a molecule are doubly occupied, the substance is diamagnetic. i.e.
that substance is repelled by an external magnetic field. If one or more M.Os are singly
occupied, it is paramagnetic. i.e. it is attracted by an external magnetic field. E.g. O2
molecule.
Molecular orbital Diagrams
The representation of various M.Os in the increasing order of energy is called M.O diagram.
Bonding in Some Homonuclear Diatomic Molecules
1. Hydrogen (H2) Molecule
H2 molecule is formed by the combination of two Hydrogen atoms.
i.e. 1H + 1H → H2
1s1 1s1
Total no. of electrons in H2 molecule = 2
So its M.O configuration is σ1s2
M.O diagram for H2 molecule is:

Due to the absence of unpaired electrons in M.Os, H2 molecule is diamagnetic.

2. Helium (He2) Molecule
He2 molecule is formed by the combination of two Helium atoms.
i.e. 2He + 2He → He2
1s2 1s 2

Total no. of electrons in He2 molecule = 4

So its M.O configuration is = σ1s2 σ*1s2
Its M.O diagram is:
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Since Nb = Na, B.O = 0 and hence He2 molecule does not exist.
3. Lithium (Li2) Molecule
Li2 molecule is formed by the combination of two Lithium atoms.
i.e. 3Li + 3Li → Li2
1s2 2s1 1s22s1
Total no. of electrons in Li2 molecule = 6
So its M.O configuration is = σ1s2 σ*1s2 σ2s2
Its M.O diagram is:

4. Carbon (C2) Molecule

C2 molecule is formed by the combination of two Carbon atoms.
i.e. 6C + 6C → C2
1s2 2s2 2p2 1s2 2s2 2p2
Total no. of electrons in C2 molecule = 12
So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 π2px2 π2py2
Its M.O diagram is:
Energy

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5. Nitrogen (N2) Molecule

N2 molecule is formed by the combination of two Nitrogen atoms.
i.e. 7N + 7N → N2
1s2 2s2 2p3 1s2 2s2 2p3
Total no. of electrons in N2 molecule = 14
So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 π2px2 π2py2 σ2pz2
Its M.O diagram is:

6. Oxygen (O2) molecule

O2 molecule is formed by the combination of two Oxygen atoms.
i.e. 8O + 8O → O2
1s2 2s2 2p4 1s2 2s2 2p4
Total no. of electrons in O2 molecule = 16
So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 π2px2 π2py2 π*2px1 π*2py1
Its M.O diagram is:

Due to the presence of unpaired electrons, O2 molecule is paramagnetic.

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7. Fluorine (F2) molecule

F2 molecule is formed by the combination of two Fluorine atoms.
i.e. 9F + 9F → F2
1s2 2s2 2p5 1s2 2s2 2p5
Total no. of electrons in F2 molecule = 18
So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 π2px2 π2py2 π*2px2 π*2py2
Its M.O diagram is:

Due to the absence of unpaired electrons, F2 molecule is diamagnetic.

Hydrogen Bonding
The weak attractive force between Hydrogen atom of one molecule and
electronegative atom (like F, O or N) of the same or different molecule is termed as
Hydrogen bond. It is weaker than a covalent bond but stronger than van der Waal’s force. It is
represented by dotted line (……….).
Cause of Hydrogen bonding: When hydrogen is bonded to a strongly electronegative atom X, the shared
electron pair is shifted more towards X. So Hydrogen atom gets a slight positive charge (δ+) and the
electronegative atom gets a slight negative charge (δ-). This results in the formation of a polar molecule.
The electrostatic force of attraction between these polar molecules is termed as H-bonding.
δ+ δ- δ+ δ- δ+ δ- δ+ δ-
…….. H-X …….. H-X ……H-X ………. H-X ……

Types of Hydrogen bonding

There are two types of H bonds- inter molecular hydrogen bonding and intra molecular hydrogen
bonding.
1) Inter molecular Hydrogen bonding: It is the hydrogen bond formed by H atom of one molecule and
the electronegative atom of another molecule.
e.g. i) Hydrogen bonding in HF
….H-F …….. H-F ……… H-F …… H-F ……

ii) H2O H–O ….. H–O…….H–O……H–O…

H H H H

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iii) NH3
H H H H
….H –N…..H–N…… H–N ....H– N….
H H H H
Inter molecular H bonding influences the physical properties of the compounds. For example water
(H2O) is a liquid with high boiling point but hydrogen sulphide (H2S) is a gas. This is because in water
inter molecular H bonding is possible which is not possible in H2S.
2) Intra molecular Hydrogen bonding: It is the hydrogen bond formed between H atom and the
electronegative atom of the same molecule.
e.g. Hydrogen bonding in ortho-nitrophenol

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5. THERMODYNAMICS
It is a branch of science that deals with the relation between heat and work. Chemical
thermodynamics is a branch of chemistry that deals with the heat changes associated with chemical
reactions.
System and Surroundings
System is the part of the universe which is under observation or investigation. The
part of the universe except system is called surroundings. The system and surroundings are
separated by a boundary which may be real or imaginary.
System + surroundings → Universe
Types of systems
Depending on the ability to exchange energy and matter with the surroundings,
systems are classified into three types:
1. Open system: It is a system that can exchange both energy and matter with the
surroundings. E.g. Hot water taken in an open vessel.
2. Closed system: It is a system that can exchange only energy and not matter with the
surroundings. E.g. Hot water taken in a closed vessel.
3. Isolated system: It is a system that cannot exchange both energy and matter with the
surroundings. E.g. Hot water taken in a thermos flask.
Depending on the number of particles, systems are of two types:
1. Microscopic system: It is a system that contains a few number of particles.
2. Macroscopic system: It is a system that contains a large number of particles.
The properties of a macroscopic system are called macroscopic properties. The important
macroscopic properties are: temperature (T), pressure (p), volume (V), length (l), breadth (b), height (h),
internal energy (U), enthalpy (H), entropy (S), Gibb’s energy (G) etc.
Macroscopic properties can be divided into two:
1. Extensive properties: These are properties which depend on the amount of matter
present in the system. Or, these are the properties which change when a system is
divided.
E.g.: Volume (V), length (l), breadth (b), height (h), internal energy (U), enthalpy (H),
entropy (S), Gibb’s energy (G), heat capacity (C) etc.
2. Intensive properties: These are properties which are independent of the amount of
matter present in the system. Or, these are the properties which do not change when a
system is divided.
E.g. : Temperature (T), pressure (p), molar volume (Vm), density, refractive index, molar
heat capacity, viscosity, surface tension etc.
State and Path functions:
A function or a property that depends only on the initial and final state of a system and
not on the path followed is called a state function.
E.g. for state functions: temperature (T), pressure (p), volume (V), internal energy (U),
enthalpy (H), entropy (S), Gibb’s energy (G) etc.
Path functions: These are properties which depend on the path followed also.
E.g. heat (q) and work (w).
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Thermodynamic process
A thermodynamic process is the method (path) by which a state change occurs in a system. The
different types of thermodynamic process are:
1. Isothermal process: It is a process that occurs at constant temperature. For this process, ΔT = 0 but
q ≠ 0. Here the system exchanges heat energy with the surroundings, in order to keep the
temperature constant.
2. Isobaric process: It is a process that occurs at constant Pressure. For such a process, Δp = 0
3. Isochoric process: It is a process that occurs at constant volume. For such a process, ΔV = 0
4. Adiabatic process: It is a process that occurs at constant heat energy. Here no heat enters into or
leaves from the system. For such a process, q= 0 but ΔT ≠ 0
5. Cyclic process: It is a process that takes place in a cyclic manner. Here the system undergoes a
series of changes and finally returns to its initial state. For such a process, ΔU=0 and ΔH = 0
6. Reversible process: Every process is associated with two types of forces – driving force and
opposing force. Driving force favours the process while opposing force opposes it. If the driving and
opposing forces are differed by an infinitesimally small quantity the process takes place in both
directions. Such a process is called reversible process.
A reversible process proceeds infinitely slowly by a series of equilibrium states such that the system
and the surroundings are always in equilibrium with each other.
7. Irreversible process: If the driving and opposing forces are differed by a large quantity, then the
process takes place in only one direction. Such a process is called irreversible process.
Heat and Work
Heat: It is a form of energy. Heat flows from a hot body to a cold body, when there is a thermal contact
between the two. When a body absorbs heat, its energy increases and when it evolves heat, its energy
decreases. Thus by international convention, when heat is absorbed by a system, q becomes +ve and
when heat is evolved by a system q becomes –ve.
Work: In thermodynamics, there are two types of work – expansion work and non-expansion work.
1. Expansion work (wexp): It is related to gaseous systems. It is the product of pressure (p) and
change in volume (ΔV). i.e., expansion work (wexp) = -pΔV
For irreversible process, (wexp) = -pΔV and
V2
For reversible process, (wexp) = -2.303nRT log
V1
2. Non-expansion work (wnon-exp): It is related to electrochemical cells. It is the product of potential
difference (E) and charge (Q). i.e., wnon-exp = E x Q
By international convention, w becomes +ve, when work is done on the system and w becomes –ve,
when work is done by the system.
Expression for pressure-volume work
Consider a cylinder fitted with a frictionless piston and contains one mole of an ideal gas.
Let the total volume of the gas is V1 and pressure of the gas inside is p.
If external pressure is pex which is greater than p, piston is moved inward till the pressure inside
becomes equal to pex. Let this change took place in a single step and the final volume be V2 .
During this compression, let the piston moves a distance l and its cross-sectional area is A.
Then, volume change, ∆V = l × A = (V2 – V1).
We know that pressure = Force/Area V1
Therefore, force on the piston = pex.A
If w is the work done on the system by movement of the piston,
then w = force × distance = pex.A.l V2 A
= pex (–∆V) = – pex ∆V = – pex (V2 – V1)

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Here the negative sign is to make the work done positive, since
(V2 – V1) is negative.
If the pressure is not constant, but changes during the process such that it is always infinitesimally
greater than the pressure of the gas, then, at each stage of compression, the volume decreases by an
infinitesimal amount, dV.
𝑉2
Then we can calculate the work done on the gas, w = – ∫𝑉1 (pex.dV)
Here, pex at each stage is equal to (pin + dp) in case of compression and (pin – dp) in case of expansion.
Generally, pex = (pin + dp). Such processes are called reversible processes.
𝑉2
Therefore, wrev = – ∫𝑉1 (pin + dp).dV
𝑉2
Since dp × dV is very small, we can write wrev = – ∫𝑉1 pin.dV
But pin = p, the pressure of the gas inside the cylinder.
𝑉2
wrev = – ∫𝑉1 p.dV
nRT
For n mol of an ideal gas i.e., pV =nRT. So p =
V
𝑉2 nRT
Thus wrev = – ∫𝑉1 . dV
V
V2
On integrating this equation, we get, wrev = –nRT ln
V1
[𝑠𝑖𝑛𝑐𝑒 ∫ 𝑉1 . 𝑑𝑉= ln V]
𝐕𝟐
On changing the base of logarithm, we can write: wrev = –2.303 nRT log
𝐕𝟏
Where n – no. of moles of the gas, R – Universal gas constant (R = 8.314 J K-1 mol-1), T – Absolute
temperature, V1 – initial volume of the gas and V2 – the final volume)
{Note: Here ln is the natural logarithm. To convert natural logarithm (base e) to common logarithm
(base 10), multiply by 2.303}.
Free expansion: Expansion of a gas into vacuum (external pressure = 0) is called free
expansion. No work is done during free expansion of an ideal gas whether the process is
reversible or irreversible.
Internal Energy (U)
Every body is associated with a definite amount of energy. This energy is called internal or
intrinsic energy. It is the energy possessed by a body. It is the sum of different types of molecular
energies like translational kinetic energy, rotational kinetic energy, vibrational kinetic energy, electronic
energy, nuclear energy etc.
Internal energy of a body is an extensive property and state function. We cannot calculate the
exact value of internal energy, but we can calculate the change in internal energy (ΔU) during a process
by using an apparatus called Bomb Calorimeter.
The change in internal energy (ΔU) = U2 – U1, where U1 and U2 are the initial and final internal
energies respectively. The unit of internal energy is kJ/mol.
The internal energy of a system can be changed in the following ways:
1. by the transfer of heat into or out of the system
2. by work done on or by the system
3. by the transfer of matter into or out of the system.
First law of thermodynamics:
It is same as law of conservation of energy. It states that energy can neither be created nor be
destroyed. Or, the total energy in the universe is always a constant. Or, the total energy
of an isolated system is always a constant.
Mathematically, ΔU = q + w ………………. (1)

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Where q is the amount of heat absorbed by the system and w is the amount of work done on the
system.
If there is only expansion work, the above equation becomes ΔU = q – pΔV ………………(2)
(since, Wexp = – pΔV)
Special cases:
➢ For isothermal (T = constant) expansion of an ideal gas into vacuum; w = 0 since p ex = 0. Also,
Joule determined experimentally that q = 0; therefore, ∆U = 0.
➢ For a system containing only solids or liquids, ΔV = 0. So, ΔU = q
➢ For an isothermal reversible process, ΔU = 0. So q = – w = 2.303nRT log(V2/V1)
➢ For an adiabatic process, q = 0, so ΔU = w.
Significance of ΔU
We know that ΔU = q – pΔV
For a process taking place at constant volume, ΔV = 0. So ΔU = qv
i.e., ΔU gives the amount of heat absorbed or evolved by a system at constant volume. It
can be measured by using a bomb calorimeter.
Enthalpy (H)
It is the total heat content of a system. It is the sum of internal energy and pressure-
volume energy of a system.
i.e. H = U + pV
It is a state function and an extensive property. i.e, whenever there is a change in enthalpy, it depends
only on the initial and final values and not on the path followed.
If H1 is the enthalpy of a system in the initial state and H2 is that in the final state, then the change in
enthalpy, ΔH = H2 – H1.
The unit of enthalpy is kJ/mol. ΔH is determined by using an apparatus called calorimeter.
For a chemical reaction, if HP is the enthalpy of products and HR is that of reactants, then
ΔH = HP – HR.
If HP > HR, ΔH is positive and heat is absorbed during the process. Such a process is called endothermic
process.
If HP < HR, ΔH is negative and heat is evolved during the process. Such a process is called exothermic
process.
Relation between ΔH and ΔU
Consider a gaseous reaction taking place at constant pressure (P) and temperature (T). Let H1, U1
and V1 be the initial enthalpy, internal energy and volume respectively. Let these values changes to H 2,
U2 and V2 respectively. Then,
H1 = U1 + pV1 ……………… (1)
And H2 = U2 + pV2 ……………… (2)
(2) – (1) gives: H2 –H1 = (U2 + pV2) – (U1 + pV1)
Or, ΔH = (U2 - U1) + (pV2 - pV1)
Or, ΔH = ΔU + p (V2 - V1)
Or, ΔH = ΔU + pΔV …… (3)
From ideal gas equation, pV = nRT [where R is the universal gas constant, R = 8.314 J K-1 mol-1]
If n1 and n2 are the total no. of moles of reactants and products respectively, then
pV1 = n1RT and pV2 = n2 RT
pV2 – pV1 = n2RT – n1RT
Or, p(V2 – V1) = (n2 – n1)RT
Or, pΔV = ΔnRT

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So equation (3) becomes, ΔH = ΔU + ΔnRT

where Δn = np(g) – nR(g)
i.e., Δn = no. of moles of gaseous products – no. of moles of gaseous reactants
If Δn =0, then ΔH = ΔU
If Δn > 0, then ΔH > ΔU
and if Δn < 0, then ΔH < ΔU.
Significance of ΔH
We know that ΔH = ΔU + PΔV (at constant pressure)
From first law of thermodynamics, ΔU = q – PΔV
So, q = ΔU + PΔV
From the above equations, we can write, ΔH = qp
i.e. enthalpy change in a chemical reaction is equal to the amount of heat evolved or
absorbed at constant pressure. This is the significance of ΔH.
Heat capacity (C)
It is the amount of heat required to raise the temperature of a body through 10C or 1K. if
q amount of heat is required to raise the temperature of a body through ΔT, then heat
q
capacity (C) = .
ΔT
Specific heat capacity is the amount of heat required to raise the temperature of unit
mass of a body through 10C or 1K.
Molar heat capacity is the amount of heat required to raise the temperature of 1 mole of a
substance through 10C or 1K.
Relation between Cp and Cv
At constant volume, the heat capacity, C is denoted by Cv and at constant pressure, it is denoted by Cp .
We know that heat, q = C ΔT
At constant volume, the heat qV = ΔU = Cv.ΔT
At constant pressure, qp = ΔH = Cp.Δ T
We know that H = U +pV
For 1 mole of an ideal gas, ΔH = ΔU + Δ(pV )
From ideal gas equation pV = nRT, for 1 mol of an ideal gas, pV = RT
So, ΔH = ΔU + Δ(RT)
Or, ΔH = ΔU + RΔT
On putting the values of ΔH and ΔU, we get
CpΔT = CvΔT + RΔT
Or, Cp = Cv + R
Or, Cp – Cv = R [This is known as Meyer’s relation]
Measurement of ∆U and ∆H - Calorimetry
We can measure energy changes associated with chemical or physical processes by an
experimental technique called calorimetry. In calorimetry, the process is carried out in a vessel called
calorimeter, which is immersed in a known volume of a liquid.
Measurement of ΔU
ΔU is measured in a bomb calorimeter. Here, a steel vessel (the bomb) is immersed in a water
bath. A combustible substance is burnt in pure dioxygen supplied in the steel bomb. Heat evolved
during the reaction is transferred to the water around the bomb. The increase in temperature is
measured by using a thermometer.
Since the bomb calorimeter is sealed, its volume does not change.
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i.e., the energy changes associated with the reaction is measured at

constant volume.
Under these conditions, no work is done as the reaction is carried
out at constant volume (i.e. ∆V = 0) in the bomb calorimeter. By knowing
the heat capacity of the calorimeter and the temperature change during
the reaction, we can calculate ∆U by the equation:
∆U = qv = Cv.∆T
Measurement of ΔH
Measurement of heat change at constant pressure (generally under
atmospheric pressure) can be done in a calorimeter. Here the reaction is
Bomb calorimeter
carried out at normal pressure and the temperature change is measured by
using a thermometer. By knowing the heat capacity of the calorimeter, we can calculate ∆H by the
equation:
ΔH = qp = Cp.∆T
∆H obtained here is also called the heat of reaction or enthalpy of reaction, ΔrH.
ENTHALPY CHANGE OF A REACTION – REACTION ENTHALPY (ΔrH)
In a chemical reaction, reactants are converted into products and is represented by,
Reactants → Products Or, R → P
The enthalpy change during a chemical reaction is called the reaction enthalpy. It is given
by the symbol ΔrH.
ΔrH = (sum of enthalpies of products) – (sum of enthalpies of reactants)
i.e. ΔrH = ∑ HP – ∑ HR
Standard enthalpy of reactions (ΔrHΘ)
The standard enthalpy of reaction is the enthalpy change for a reaction when all the
substances are in their standard states. In thermodynamics, the standard state refers to
the existence of a substance in its pure form at 1 bar pressure and 298 K temperature.
Standard enthalpy of formation (ΔfHΘ)
It is the standard enthalpy change for the formation of one mole of a compound
from its elements in their most stable state of aggregation (or, reference state). It is
denoted by the symbol ΔfHΘ. For e.g. the std. enthalpy of formation of CO2 is the enthalpy change
when 1 mole of CO2 is formed from C and O2 at 298K temperature, 1 bar pressure and all the substances
are in their stable state.
The reference state of an element is its most stable state at 25°C and 1 bar pressure. The
reference state of dihydrogen is H2 gas and those of dioxygen, carbon and sulphur are O2 gas, Cgraphite
and SRhombic respectively. The enthalpy of formation may be positive or negative.
By convention, standard enthalpy of formation (ΔfHΘ) of an element in reference state ( i.e., its
most stable state of aggregation) is taken as zero.
By knowing the std. enthalpies of formation of reactants and products, we can determine the
std. enthalpy of reaction by the equation: ΔrHΘ = ∑ ΔfHΘ(P) - ∑ ΔfHΘ(R)
i.e. std. enthalpy of reaction = sum of the standard enthalpies of formation of products – sum of
the std. enthalpies of formation of reactants.
Enthalpies of phase transition
It is the enthalpy change when one mole of a substance changes from one phase to another
phase at a particular temperature. The important types of Enthalpies of phase transition are:

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1) Molar Enthalpy of fusion (ΔfusHΘ): It is the enthalpy change when one mole of a solid substance
changes to liquid state at its melting point.
2) Molar Enthalpy of vaporization (ΔvapHΘ): It is the enthalpy change when one mole of a liquid
substance changes to its vapour state at its boiling point.
3) Molar Enthalpy of sublimation (ΔsubHΘ): It is the enthalpy change when one mole of a solid
substance is directly converted to gaseous state at a particular temperature below its m.p.
Enthalpies of fusion, vaporization and sublimation are positive, since heat is absorbed during
these process. The magnitude of the enthalpy change depends on the strength of the intermolecular
forces in the substance.
Thermochemical equations
A balanced chemical equation together with the value of enthalpy of reaction is called a
thermochemical equation. Here the physical state of the each of the reactants and products is also
shown in bracket.
e.g. H2(g) + ½ O2(g) → H2O(g), ΔrHΘ = -285.83 kJ/mol
or, H2(g) + ½ O2(g) → H2O(g) + 285.83 kJ/mol
When we multiply or divide a thermochemical equation with a number, then ΔrHΘ is also multiplied or
divided with the same number.
For e.g. N2(g) + 3H2(g) → 2NH3 (g); ΔrHΘ = – 91.8 kJ/mol
Then, ½ N2(g) + 3⁄2 H2(g) → NH3(g); ΔrHΘ = – 45.9 kJ/mol
When a chemical equation is reversed, the value of ΔrHΘ is reversed in sign.
For e.g. N2(g) + 3H2(g) → 2NH3 (g); ΔrHΘ = – 91.8 kJ/mol
Then, 2NH3(g) → N2(g) + 3H2(g); ΔrHΘ = + 91.8 kJ/mol
Hess’s Law of Constant Heat Summation
The law states that the total enthalpy change for a physical or chemical process is
the same whether the reaction taking place in a single step or in several steps.
Or, the total enthalpy change for a process is independent of the path followed.
Thus 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.
Illustration:
Consider a process in which the reactant A is converted to product B
in a single step by involving heat change ΔH. Let the same reactant A
is first converted to C, then to D and finally to B involving heat changes
ΔH1, ΔH2 and ΔH3 respectively.
Then according to Hess’s law: ΔH = ΔH1 + ΔH2 + ΔH3
Standard enthalpy of combustion (ΔcHΘ)
It is defined as the enthalpy change when 1mole of a substance is completely burnt in presence
of excess of air or oxygen and all the reactants and products being in their standard states. It is always
negative since heat is always evolved during combustion.
e.g. CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g)
Enthalpy of atomization (ΔaHΘ)
It is the enthalpy change on breaking one mole of bonds completely to obtain atoms in the gas
phase. In the case of diatomic molecules the enthalpy of atomization is same as the bond dissociation
enthalpy.
E.g. H2(g) → 2H(g); ΔaHΘ = 435.0 kJ mol–1

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Bond Enthalpy (ΔbondHΘ)

Chemical reactions involve the breaking and making of chemical bonds. Energy is required
to break a bond and energy is released when a bond is formed. So enthalpy of bond dissociation is
positive and enthalpy of bond formation is negative.
The amount of heat required to break one mole of covalent bonds to form products in the gas
phase is called the bond dissociation enthalpy. For diatomic molecules, bond dissociation enthalpy and
bond enthalpy are same.
e.g. H2(g) → 2H(g); ΔbondHΘ = 435.0 kJ mol–1
In the case of polyatomic molecules, bond dissociation enthalpy is different for different
bonds within the same molecule. So here bond enthalpy is the average of bond dissociation enthalpies
of various similar bonds.
For e.g. for water, the bond enthalpy is calculated as follows:
H2O(g) → H(g) + OH(g); ΔaHΘ = 502 kJ/mol
OH(g) → O(g) + H(g); ΔaHΘ = 427 kJ/mol
Here the bond enthalpy of O-H bond is taken as the average of the two bond dissociation enthalpies.
502+427
i.e. bond enthalpy of O-H bond = = 464.5kJ/mol
2
The standard enthalpy of reaction, ΔrH0 is related to bond enthalpies of the reactants and products in
gas phase reactions as:
ΔrHΘ = ∑ bond enthalpies of reactants - ∑ bond enthalpies of products
This equation is valid when all the reactants and products in the reaction are in gaseous state.
Enthalpy of Solution (ΔsolHΘ)
Enthalpy of solution is the enthalpy change when one mole of a substance is
dissolved in a specified amount of solvent.
The enthalpy of solution in water is determined by the values of the lattice enthalpy, ΔlatticeHΘ
and enthalpy of hydration of ions, ΔhydHΘ.
i.e. ΔsolHΘ = ΔlatticeHΘ + ΔhydHΘ
For most of the ionic compounds, ΔsolHΘ is positive and the dissociation process is endothermic.
Therefore the solubility of most salts in water increases with rise of temperature.
If the lattice enthalpy is very high, the dissolution of the compound may not take place at all.
Fluorides of many metals are less soluble than the corresponding chlorides, because of
their higher lattice enthalpies.
Lattice Enthalpy (ΔlatticeHΘ)
The lattice enthalpy of an ionic compound is the enthalpy change when one mole of
an ionic compound dissociates into gaseous ions.
We cannot determine lattice enthalpies directly by experiment. So an indirect method called
Born-Haber Cycle is used to calculate lattice enthalpy of a compound.
This can be explained by consider the formation of NaCl.
Na(s) + ½ Cl2(g) → NaCl(s)
This involves the following steps:
1. Conversion of solid sodium atom to gaseous sodium atom. The energy change involved in this
process is called sublimation energy.
Na(s) → Na(g); ΔsubHΘ
2. Conversion gaseous sodium atom to gaseous sodium ion. The energy change in this process is
called ionisation enthalpy.
Na(g)→ Na+(g); ΔiHΘ
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3. Conversion of gaseous chlorine molecule to gaseous chlorine atom. The energy change during
this process is called bond dissociation enthalpy.
Cl2(g)→ 2Cl(g); ΔbondHΘ
½ Cl2(g) → Cl(g); ½ ΔbondHΘ
4. Conversion of chlorine atom to chloride ion. The energy change involved in this process is called
electron gain enthalpy (ΔegHΘ).
Cl(g) → Cl-(g); ΔegHΘ
5. Packing of Na+(g)and Cl-(g) to form NaCl(s). the energy change in this process is called lattice
enthalpy (ΔlatticeHΘ)
Na+(g) + Cl-(g) → NaCl(s); ΔlatticeHΘ
The different steps can be represented in a cyclic for as follows:

By applying Hess’s law we can write: ΔfHΘ = ΔsubHΘ + ΔiHΘ + ½ ΔbondHΘ + ΔegHΘ+ ΔlatticeHΘ
Form this lattice enthalpy can be determined as:
ΔlatticeHΘ = ΔfHΘ – [ΔsubHΘ + ΔiHΘ + ½ ΔbondHΘ + ΔegHΘ]
Enthalpy of Dilution (ΔdilHΘ):
It is the enthalpy change when a solution is diluted (i.e. more solvent is added to the solution. It
depends on the original concentration of the solution and the amount of solvent added.
Spontaneous Process
It is a process that takes place without the help of any external agency. All natural
processes are spontaneous. E.g. flow of water from high level to low level, flow of heat from hot body
to cold body, inter mixing of gases, burning of fuels, melting of ice, evaporation of water etc. A
spontaneous process cannot reverse its direction by its own.
Spontaneous chemical reactions are also called feasible or probable or irreversible reactions.
e.g. N2 + 3H2 → 2NH3; ΔrHΘ = - 46.1kJ/mol
2H2 + O2 → 2H2O; ΔrHΘ = - 285.8 kJ/mol
A process that takes place with the help of an external agency is called non-spontaneous
process. E.g. flow of water from low level to high level.
Criteria for spontaneity
During spontaneous processes like burning of fuels, flow of heat from hot body to cold body,
flow of water from high level to low level etc, energy of the system decreases. So one of the criteria
for spontaneity is decrease in energy.
But for some spontaneous processes like melting of ice, evaporation of water etc, heat is
absorbed. i.e. the energy of the system increases during the process. The above processes are

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accompanied with increase in disorder (entropy) of the system. Thus another criterion for
spontaneity is increase in disorderness or randomness of the system.
Entropy (S)
It is a measure of degree of disorderness or randomness of a system. As the
disorderness increases, entropy also increases. It is an extensive property and state function.
If S1 is the initial entropy of a system and S2 is its final value, then the change in entropy ∆S = S2 –S1.
For a given substance, the solid state has the least entropy and the gaseous state
has the most. When temperature increases entropy also increases. The unit of entropy and
entropy change is J/K/mol.
If a system absorbs ‘q’ amount of heat reversibly at a temperature T, then the change in entropy,
qrev
∆S = , where qrev. is the amount of heat absorbed reversibly.
T
Entropy and spontaneity
During a spontaneous process, disorderness of the system increases. Thus entropy increases and
hence ∆S becomes positive.
The total entropy change for the system and surroundings is given by ∆S Total = ∆Ssyst. + ∆Ssurr.
For a spontaneous process, ∆STotal > 0
When a system attains equilibrium, the entropy becomes maximum and there is no
further change in entropy. So ∆S Total = 0
If ∆S Total < 0, the process is non-spontaneous.
Second Law of Thermodynamics:
It can be stated as the entropy of the universe always increases during every
spontaneous process.
Third law of Thermodynamics:
It states that the entropy of any perfectly crystalline substance is zero at absolute
zero of temperature. By using this law, we can calculate the absolute value of entropy of pure
substances from their thermodynamic data.
Gibb’s energy (G)
It is defined as the maximum amount of available energy that can be converted to
useful work. It is given by the equation, G = H – TS
It is an extensive property and a state function.
If G1 is the initial Gibb’s energy and G2 is its final value, then the change in Gibb’s energy (∆G) = G2 – G1
The unit of Gibb’s energy is kJ/mol.
Relation between ∆G, ∆H and ∆S (Gibb’s Equation)
We know that G = H – TS
So, ∆G = ∆H – ∆(TS)
= ∆H – (T∆S + S∆T)
At constant temperature, ∆T = 0.
So, ∆G = ∆H - T∆S. This equation is known as Gibb’s equation.
At standard state, ∆GΘ = ∆HΘ - T∆SΘ
The change in Gibb’s energy for a system can be written as
∆Gsyst. = ∆Hsyst. - T∆Ssyst.

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Gibb’s energy and Spontaneity

We know that ∆STotal = ∆Ssyst. + ∆Ssurr. ……….. (1)
Consider a system which absorbs ‘q’ amount of heat reversibly at a constant temperature T and
constant pressure p.
qp
Then, ∆Ssurr. =
T
But qp = ∆Hsurr. and ∆Hsurr. = -∆Hsyst.
−ΔHsyst
So, ∆Ssurr. =
T
ΔHsyst
So equation (1) becomes, ∆STotal = ∆Ssyst. –
T
On multiplying by –T, we get
-T∆STotal = -T∆Ssyst. + ∆Hsyst.
Or, -T∆STotal = ∆Gsyst. (Since, ∆H syst. - T∆Ssyst. = ∆Gsyst.)
For a spontaneous process, ∆STotal is positive. So ∆Gsyst. is negative. (or, ∆Gsyst. < 0)
For a non-spontaneous process, ∆STotal is negative, so ∆Gsyst. is positive. (or, ∆Gsyst. > 0)
For a process at equilibrium, ∆STotal = 0. So ∆Gsyst. = 0
Conditions for ∆G to be negative
We know that for a spontaneous process, ∆Gsyst. is negative. Also ∆G = ∆H - T∆S.
1) If ∆H is negative and ∆S is +ve, ∆G is always –ve and the process is always spontaneous.
2) If both ∆H and ∆S are positive, ∆G will be –ve when T∆S > ∆H. This is possible at high
temperature. i.e. the process will be spontaneous at higher temperature. E.g. melting of ice.
3) If both ∆H and ∆S are negative, ∆G will be –ve when T∆S < ∆H. This is possible at low
temperature. i.e. the process will be spontaneous at lower temperature. E.g. Condensation of
water-vapour.
Note: If ∆H is +ve and ∆S – ve, then ∆G will be always +ve and the process will be always non-
spontaneous.
Gibb’s energy change (∆G) and Equilibrium constant (K)
Consider a reversible reaction: A + B ⇌ C + D
The Gibb’s energy change of this reaction is ∆rG = ∆rGΘ + RT ln K
At equilibrium, ∆rG = 0
So, 0 = ∆rGΘ + RT ln K
Or, ∆rGΘ = – RT lnK
Or, ∆rGΘ = – 2.303RT logK
Where R is the universal gas constant and T is the absolute temperature. [R = 8.314 J K-1mol-1]
So for a spontaneous process, the value of K should be positive.
======================================================================================================
Q1) The equilibrium constant for a reaction is 5. What will be the value of ∆G0?
Given that R = 8.314 J K-1m Find the temperature above which the reaction
MgO(s) + C(s) → Mg(s) + CO(g) becomes spontaneous. (Given ∆rH0 = 490 kJ mol-1 and
∆rS0 = 198 JKmol-1).ol-1, T = 300K.
Ans: ∆G0 = -2.303RTlogK
= -2.303 x 8.314 x 300 x log5 = – 4014.58 J mol-1

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Q2) For the reaction, 4Fe(s) + 3O2(g) →2 Fe2O3 (s), the entropy change is - 549.4 J
K-1 mol-1 at 298 K. Inspite of the negative entropy change, why is the reaction
spontaneous? Given ∆Ho = - 1648 kJ mol-1.
Ans: We know that ∆G0 = ∆H0 - T∆S0
Here ∆Ho = - 1648 kJ mol-1 = -1648 x 103 J/mol. ∆So = - 549.4 J K mol-1 and T = 298 K
So, ∆G0 = -1648 x 103 – 298 x -549.4 = –1811.72 x 103 J mol-1
Q3) Calculate the work done for the reversible isothermal expansion of 1 mole of
an ideal gas at 270C, from a volume of 10 dm3 to a volume of 20 dm3.
Ans: Here n = 1 mol, R = 8.314 J/K/mol, V1 = 10 dm3, V2 = 20 dm3 and T = 25 + 273 = 298 K
𝑉
For isothermal reversible expansion, work done, wexp = -2.303nRT log 𝑉2
1
20
= -2.303 x 1 x 8.314 x 298 x log 10
= -1717.46 J
Q4) Find the temperature above which the reaction MgO(s) + C(s) → Mg(s) + CO(g)
becomes spontaneous. (Given ∆rH0 = 490 kJ mol-1 and ∆rS0 = 198 JKmol-1).
Ans: At equilibrium, ∆rG0 = 0
So the Gibb’s equation, ∆rG0 = ∆rH0 - T∆rS0 becomes:
0 = ∆rH0 - T∆rS0
Or, ∆rH0 = T∆rS0
So, T = ∆rH0/∆rS0 = 490 x 103/198 = 2474.74K.
So at 2474.74K, the reaction is at equilibrium.
Above this temperature, the reaction becomes spontaneous. [Here both ΔrH0 and ΔrS0 are +ve. So
ΔrG0 becomes –ve only when TΔrS0 > ΔrH0. This is possible at high temperature.]
Q5) The enthalpy of combustion of CH4(g), C(graphite) and H2(g) at 298K are -890.3 kJ
mol-1, -393.5 kJ mol-1 and -285.8 kJ mol-1 respectively. Calculate the enthalpy of
formation of CH4(g).
Ans: The required equation is: C(graphite) + 2H2(g) → CH4(g)
The given data are: CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l); ∆H = -890.3 kJ/mol ………… (i)
C(graphite) + O2(g) → CO2(g); ∆H = -393.5 kJ/mol …………………….. (ii)
H2(g) + ½ O2(g) → H2O(l); ∆H = -285.8 kJ/mol …………………………. (iii)
Multiply equation (iii) x 2: 2H2(g) + O2(g) → 2 H2O(l); ∆H = -285.8 x 2 = -571.6 kJ/mol …… (iv)
Reverse equation (i): CO2(g) + 2H2O(l) → CH4(g) + 2 O2(g); ∆H = 890.3 kJ/mol ……….. (v)
Now add the equations (ii) + (iv) + (v) we get C(graphite) + 2H2(g) → CH4(g); ∆H = -393.5 + -571.6 +
890.3 = -74.8 kJ/mol
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6. EQUILIBRIUM
Reversible and irreversible reactions
A reaction that takes place in only one direction is called an irreversible reaction.
e.g. Reaction between NaOH and HCl
NaOH + HCl → NaCl + H2O
Reversible reactions are those which take place in both directions. i.e. here reactants
combined to form products and the products recombine to form reactants.
E.g. Haber process for the preparation of ammonia.
N2(g) + 3H2(g) 2NH3(g)
The process by which reactants are converted to products is called forward reaction and the
process by which products recombine to form reactants is called backward reaction. After sometimes,
the rate of forward reaction becomes equal to the rate of backward reaction and the reaction attains
equilibrium. Thus equilibrium is a state in which the rates of forward and backward reactions are equal.
Equilibrium is dynamic in nature. i.e. at equilibrium the reaction does not stop. The
reactant molecules collide to form products and the product molecules collide to form the
reactants and the rates of these reactions are equal.
Physical equilibrium
Equilibrium involving physical process is called physical equilibrium. E.g. melting of ice,
evaporation of water, sublimation, dissolution of solids or gases in liquids etc.
1. Solid-Liquid Equilibrium
When ice and water are kept in a perfectly insulated thermos flask at 273K and 1 atm pressure,
there exist an equilibrium between ice and water. i.e. ice is converted to water (melting or fusion) and
water is converted to ice (freezing) at the same rate. At this stage, there is no change in the mass of ice
and water.
H2O(s) ⇌ H2O(l)
Ice and water are in equilibrium only at particular temperature and pressure. For any pure
substance at atmospheric pressure, the temperature at which the solid and liquid phases are at
equilibrium is called the normal melting point or normal freezing point of the substance.
2. Liquid-Vapour Equilibrium
Water and water vapour are in equilibrium position at atmospheric pressure (1.013 bar) and at
100°C in a closed vessel. At this stage, the conversion of water to water-vapour [evaporation] and the
reverse process [condensation] takes place in equal rates.
H2O(l) ⇌ H2O(g)
For any pure liquid, the temperature at which the liquid and vapours are at equilibrium at one
atmospheric pressure (1.013 bar), is called normal boiling point of the liquid. The normal boiling point
of water is 100°C.
Boiling point of the liquid depends on the atmospheric pressure. It also depends on the altitude
of the place. At high altitude the boiling point decreases.
3. Solid – Vapour Equilibrium
If we place solid iodine in a closed vessel, after sometimes the vessel gets filled up with violet
vapour and the intensity of colour increases with time. After certain time the intensity of colour
becomes constant and at this stage, equilibrium is attained. I2(solid) ⇌ I2 (vapour)
4. Dissolution of Solid in Liquids
Consider the dissolution of sugar in a fixed amount of water. When we add sugar into water, at
first, we can dissolve more amount of sugar, since the solution is unsaturated. But after sometime, the

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rate of dissolution of sugar decreases and rate of its crystallisation increases. i.e. the sugar molecules in
the solution separate out as solid sugar. At equilibrium state, the rate of dissolution becomes equal to
the rate of crystallisation. At this stage, the solution is called saturated solution. It is a solution in which
no more solute can be dissolved at a given temperature. The concentration of the solute in a saturated
solution depends upon the temperature.
Sugar (solution) ⇌ Sugar (solid)
5. Dissolution of Gases in Liquids
The solubility of a gas in a liquid depends on nature of the gas, pressure of the gas and
temperature. When pressure of the gas increases, its solubility also increases. A quantitative relation
between pressure and solubility was proposed by Henry and is known as Henry’s law. The law states
that the mass of a gas dissolved in a given mass of a solvent is proportional to the
pressure of the gas above the solvent, at a constant temperature.
In soda water, CO2 gas is dissolved in water at high pressure. There is an equilibrium between the
CO2(g) in the solution and that in the free state above the solution.
i.e., CO2 (gas) ⇌ CO2 (in solution)
When the bottle is opened, some of the dissolved carbon dioxide gas, escapes out with a fizzing
sound and a new equilibrium at low pressure is attained.
The solubility of a gas in a liquid decreases with increase in temperature.
General Characteristics of Physical Equilibrium
(i) Equilibrium is possible only in a closed system at a given temperature.
(ii) Both the opposing processes (forward and backward processes) occur at the same rate and
there is a dynamic but stable condition.
(iii) All measurable properties of the system remain constant at equilibrium.
(iv) When equilibrium is attained for a physical process, it is characterised by constant value of
one of its parameters at a given temperature.
(v) The magnitude of such quantities at any stage indicates the extent to which the physical
process has proceeded before reaching equilibrium.
Chemical Equilibrium
Equilibrium associated with chemical reactions is called chemical equilibrium. At equilibrium, the
concentrations of reactants and products are constant.
Consider a hypothetical reaction, A + B ⇌ C + D
As the reaction proceeds, the concentration of the reactants decreases and that of the products
increases. After sometimes, the two reactions occur at the same rates and an equilibrium state is
reached. This can be illustrated by the following graph.

After the equilibrium is attained, the concentration of the reactants and products become
constant. At equilibrium, the rate of forward reaction (rf) = the rate of backward reaction (rb).

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Law of Chemical Equilibrium and Equilibrium Constant

This law was proposed by Guldberg and Waage. It states that at constant temperature, the
product of concentration of the products to that of the reactants, in which each concentration terms is
raised to a power which is equal to the stoichiometric coefficients in the balanced chemical equation, has
a constant value.
For a general reversible reaction:
A+B ⇌C+D
[C][D]
According to the equilibrium law, = Kc
[A][B]
Where Kc is called the equilibrium constant.
For a general reaction, aA + bB ⇌ cC + dD,
[C]c [D]d
Kc =
[A]a [B]b
[HI]2
For the reaction H2 + I2 ⇌ 2HI; Kc =
[H2 ][I2 }
[𝑁𝐻3 ]2
For the reaction N2 + 3H2 ⇌ 2NH3; Kc =
[N2 ][H2 ]3
Equilibrium constant for the reverse reaction is the inverse of that for the forward reaction.
i.e. if the equilibrium constant for the reaction: H2 + I2 ⇌ 2HI is Kc,
1
then that for the reverse reaction: 2HI ⇌ H2 + I2 is .
Kc
Equilibrium constant for gaseous reactions
For a reaction involving gases, the concentration terms are replaced by partial pressures.
p2HI
For example, H2(g) + I2(g) ⇌ 2HI(g); Kp =
pH2 pI2
Where Kp is called equilibrium constant in terms of partial pressure, pHI, pH2 and pI2 are the partial
pressures of HI, H2 and I2 respectively.
Relation between Kc and Kp
Consider a general reaction, aA + bB ⇌ cC + dD
[C]c [D]d
The equilibrium constant in terms of concentration for this reaction is Kc = ……… (1)
[A]a [B]b
pcC .pd
D
And the equilibrium constant in terms of partial pressures is Kp = …………(2)
paA .Pb
B
nRT
From ideal gas equation, pV = nRT, p = = CRT (since n/V = C, the concentration)
V
Therefore, pA = CART, pB = CBRT, pC = CCRT and pD= CDRT
Substitute these values in equation (2), we get
(𝐶𝑐 𝑅𝑇)𝑐 (𝐶𝐷 𝑅𝑇)𝑑
Kp =
(𝐶𝐴 𝑅𝑇)𝑎 ⬚ (𝐶𝐵 𝑅𝑇)𝑏
CcC .Cd
D (RT)
c+d
Or, Kp =
CaA .Cb
B (RT)
a+b

CcC .Cd
D
Or, Kp = (RT)(c+d)−(a+b)
CaA .Cb
B
[C]c [D]d
Or, Kp = Kc.(RT)∆n, where Kc =
[A]a [B]b
And ∆n is the change in no. of moles of gaseous species.
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i.e. ∆n = no. of moles of gaseous products – no. of moles of gaseous reactants.

Special cases:
i) If ∆n = 0, then Kp = Kc
ii) If ∆n > 0, then Kp > Kc and
iii) If ∆n < 0, then Kp < Kc
Homogeneous and heterogeneous equilibria
Equilibrium reaction in which all the reactants and products are in the same phase is called
homogeneous equilibrium.
E.g. N2(g) + 3H2(g) ⇌ 2NH3(g)
2SO2(g) + O2(g) ⇌ 2SO3(g)
Equilibrium reaction in which the reactants and products are in different phases is called
heterogeneous equilibrium.
E.g. CaCO3(s) ⇌ CaO(s) + CO2(g)
H2O (s) ⇌ H2O(l)
Characteristics of Equilibrium constant
The important characteristics of equilibrium constant are:
1. Equilibrium constant is applicable only when the concentrations of the reactants and products
have attained their equilibrium state.
2. The value of equilibrium constant is independent of the initial concentrations of reactants and
products.
3. The value of equilibrium constant depends on temperature.
4. The equilibrium constant for the reverse reaction is the reciprocal of that of the forward
reaction.
5. If for the reaction A ⇌ B, the value of equilibrium constant is K, then for the reaction nA ⇌ nB,
its value is Kn.
Applications of Equilibrium constant
The important applications of equilibrium constant are:
1. Prediction of the extent of a reaction
Greater the value of equilibrium constant, greater will be the concentration of products. In general,
a) If Kc > 103 (i.e. Kc is very large), the reaction proceeds nearly to completion
b) If Kc < 10-3 (i.e. if Kc is very small), the reaction proceeds rarely.
c) If the value of Kc is in between 103 and 10-3 appreciable concentrations of both reactants and
products are present.
2. Prediction of the direction of the reaction
By knowing the values of Kc and Qc, we can predict the direction of a reaction. The reaction
quotient(Qc) is defined in the same way as the equilibrium constant (Kc) except that the concentrations
in Qc are not necessarily the equilibrium values.
[C]c [D]d
For a general reaction, aA + bB ⇌ cC + dD, the reaction quotient, Qc =
[A]a [B]b
If Qc > Kc, the reaction will proceed in the direction of reactants (reverse direction).
If Qc < Kc, the reaction will proceed in the direction of products (forward direction).
If Qc = Kc, the reaction mixture is at equilibrium.
3. Calculation of equilibrium concentrations
By knowing the value of equilibrium constant, we can calculate the equilibrium concentrations of
reactants and products.

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RELATIONSHIP BETWEEN EQUILIBRIUM CONSTANT (KC), REACTION QUOTIENT (QC) AND

GIBBS ENERGY CHANGE (ΔG)
The Gibb’s energy change of a reaction is related to the reaction quotient (Qc) by the equation:
ΔG = ΔG0 + RT lnQc
where, ΔG0 is standard Gibbs energy change.
At equilibrium, ΔG = 0 and Qc = Kc, so the equation becomes,
0 = ΔG0 + RT ln Kc
Or, ΔG0 = – RT lnKc
On changing the base, we get ΔG0 = – 2.303RT logKc
We know that for a spontaneous process ΔG should be negative. So the value of Kc should be positive.
Factors affecting equilibrium
The important factors affecting equilibrium are temperature, pressure, concentration and catalyst.
The effect of these factors on equilibrium state can be explained by using Le Chartier’s Principle.
It states that whenever there is a change in concentration, pressure or temperature of a
system at equilibrium, the system will try to readjust in such a way so as to cancel the
effect of that change.
1. Effect of concentration change
If we change the concentration of reactants or products in an equilibrium process, then according
to Le Chatelier’s principle, the system will try to reduce the effect of that change. For this the rate of
either forward or backward reaction changes.
In general, an increase in concentration of reactants increases the rate of forward reaction (i.e.
the equilibrium is shifted to the products side) and an increase in concentration of products increase the
rate of backward reaction (i.e. the equilibrium is shifted to the reactants side).
For example in the reaction 2SO2(g) + O2(g) ⇌ 2SO3(g), if we increase the concentration of SO2 or
O2, the system will try to reduce the concentration by shifting the equilibrium to the forward direction.
If we remove SO3 from the reaction mixture, its concentration decreases. To increase the concentration,
the equilibrium is shifted to the forward direction.
In Haber process for the preparation of ammonia, the amount of ammonia formed can be
increased by increasing the concentration of N2 or H2 or by removing NH3 from the reaction mixture.
2. Effect of temperature change
According to Le Chatelier’s principle, increase in temperature favours endothermic process and
decrease in temperature favours exothermic process. In a reversible reaction, if the forward reaction is
endothermic, the backward reaction will be exothermic.
E.g.: N2(g) + 3H2(g) ⇌ 2 NH3(g); ∆H = -92.38kJ/mol
Here since ∆H is negative, the forward reaction is exothermic. So to increase the production of
NH3, temperature should decrease. At higher temperature, the rate of backward reaction increases. i.e.
the ammonia formed is decomposed to N2 and H2.
3. Effect of pressure change
Pressure has its effect only in gaseous reactions. In general, an increase in pressure favours the
reaction in which number of moles decreases and vice versa.
Thus in the reaction, N2(g) + 3H2(g) ⇌ 2 NH3(g), when the pressure increases, the system will try to reduce
the pressure. This can be achieved by shifting the reaction into the direction in which no. of moles
decreases (since pressure is directly proportional to the number of moles). So in this reaction, the
equilibrium will shift to the forward direction.
If the volume of the reaction mixture is halved, the concentration and the partial pressure become
doubled. So the reaction is shifted to the direction in which the number of moles or volume decreases.

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4. Effect of catalyst
A catalyst is a substance that increases the rate or speed of a chemical reaction.
In an equilibrium reaction, a catalyst increases the rate of both forward and backward reactions
simultaneously and helps to attain the equilibrium faster. It lowers the activation energy for the forward
and backward reactions by exactly the same amount. It does not affect the equilibrium composition of
the reaction mixture.
Thus in Haber process for the manufacture of ammonia, spongy iron (Fe) acts as the catalyst. In contact
process for the manufacture of sulphuric acid, V2O5 (Vanadium pentoxide) is used as the catalyst.
5. Effect of inert gas addition
If an inert gas (which does not take part in the reaction) is added to an equilibrium mixture at
constant volume (or, at constant pressure), there is no change to the equilibrium. It is because the
addition of inert gas at constant volume (or, at constant pressure) does not change the partial pressure
or the concentration of the reactants and the products.
Ionic equilibrium in solution
Equilibrium involving ions is called ionic equilibrium. E.g. dissociation of acetic acid in water.
CH3COOH + H2O ⇌ CH3COO- + H3O+
Electrolytes and non-electrolytes
Based on the ability to conduct electricity, Michael Faraday divided substances into two –
electrolytes and non-electrolytes.
Electrolytes are substances which conduct electricity in molten state or in solution state.
E.g. All acids, bases and almost all salts
Non- electrolytes are substances which do not conduct electricity in molten state or in solution state.
E.g. sugar, urea etc.
Electrolytes are further classified into two - strong electrolytes and weak electrolytes.
Strong electrolytes are electrolytes which dissociate almost completely in aqueous solution.
E.g. strong acids like HCl, HNO3, H2SO4 etc., strong bases like NaOH, KOH etc. and salts like NaCl, KCl,
Na2SO4, K2SO4, KNO3, NaNO3 etc.
Electrolytes which dissociate only partially in aqueous solution are called weak electrolytes. E.g.
weak acids like acetic acid [CH3COOH], formic acid [HCOOH] etc., weak bases like Mg(OH)2, Ca(OH)2,
NH4OH etc. and some salts like CaSO4, BaSO4 etc.
A weak electrolyte dissociates only partially in aqueous solution and so an equilibrium is formed
between the ions and the unionised molecules. This type of equilibrium, which involve ions in aqueous
solution is called ionic equilibrium.
Acids, Bases and Salts
Acid – base concepts:
1. Arrhenius concept: According to this concept, acids are substances which give
hydrogen ion (H+) or hydronium ion (H3O+) in aqueous solution and bases are
substances which give hydroxyl ion (OH–) in aqueous solution.
E.g. HCl is an acid since it produces H3O+ in aqueous solution.
HCl(l) + H2O(l) ⇌ H3O +(aq) + Cl– (aq)
E.g. for base is NaOH
NaOH(s) + H2O(l) ⇌ Na+(aq) + OH– (aq)
Note: H ions exist in water as hydronium ions (H3O+)
+

H+ + H2O ⇌ H3O+
Limitations: This concept is applicable only to aqueous solutions.

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2. The Bronsted – Lowry concept:

According to this concept acids are proton (H+) donors and bases are (H+) acceptors.
For example in the reaction NH3(l) + H2O(l) ⇌ NH4+(aq) + OH– (aq)
Here NH3 is a base since it accepts an H+ ion to form NH4+ and H2O is an acid since it donates an
H+ ion to form OH– . In the reverse reaction, NH4+ is an acid and OH- is a base.
The acid-base pair that differs by only one proton is called a conjugate acid–base pair.
An acid formed from a base is called conjugate acid and a base formed from an acid is called conjugate
base.
For example

In general, Conjugate base = Acid – H+

Conjugate acid = Base + H+
HCl + H2O ⇌ H3O+ + Cl–
Acid base conj. acid conj. Base
If the acid is strong, its conjugate base is weak and vice versa. So in the above example Cl – is a
weak conjugate base of the strong acid HCl.
Water can act both as acid and base. So it is an amphoteric substance.
e.g. NH3 + H2O ⇌ NH4+ + OH–
acid
HNO3 + H2O ⇌ H3O+ + NO3–
base
3. Lewis concept:
According to this concept acids are electron pair acceptors and bases are electron pair
donors. Substances which donate electron pair are called Lewis bases and substances which accept
electron pair are called Lewis acids.
Example for Lewis acids are BF3, AlCl3, H+, Co3+, Mg2+ etc.
Example for Lewis bases are NH3, H2O, OH–, Cl–, Br– etc.
For a substance to act as Lewis acid, it should contain vacant orbitals and for a substance to act
as Lewis base, it should contain lone pairs of electrons.
E.g. for acid – base reaction is BF3 + NH3 → BF3←NH3
All cations are Lewis acids and all anions are Lewis bases.
The ionization constant of water (The ionic product of water)
Water is a weak electrolyte and hence it ionizes only partially as:
H2O ⇌ H+ + OH-
Or, H2O + H2O ⇌ H3O+ + OH-
[H+ ][OH− ] [H3 O+ ][OH− ]
The dissociation constant, K = or, K =
[H2 O] [H2 O]
Or, K.[H2O] = [H+][OH–]
Or, Kw = [H+][OH-] or, Kw = [H3O+][OH-] Where Kw = K.[H2O], the ionization constant of water or ionic
product of water. It is defined as the product of the molar concentration of hydrogen ion (hydronium ion)
and hydroxyl ion in water or in any aqueous solution.

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For pure water at 298K, [H+] = [OH-] = 10-7M.

Therefore, Kw = [H+][OH-] = 10-7 x 10-7 = 10-14 M2
The value of Kw is temperature dependent.
By knowing the concentrations of H3O+ and OH- ions, we can predict the nature of an aqueous solution.
If [H3O+] > [OH-], the solution is acidic
If [H3O+] < [OH-], the solution is basic
If [H3O+] = [OH-], the solution is neutral
The pH scale
pH is defined as the negative logarithm of the hydrogen ion or hydronium ion
concentration in moles per litre (i.e. molarity).
i.e. pH = - log[H+] or pH = - log[H3O+]
Negative logarithm of hydroxyl ion concentration in mol/L is called p OH.
i.e. pOH = – log[OH-]
For pure water, at 298K (250c), [H+] = 10-7. Therefore pH of pure water is 7.
The pH scale was introduced by Sorensen. It contains numbers from 0 to 14. If the pH is less than
7, the solution is acidic, if it is greater than 7, it is basic and if it is 7, the solution is neutral.
If the pH is 0, 1, 2 etc., the solution is a strongly acidic and if it is 12, 13, 14 etc, it is strongly basic.
H
The p of our blood is 7.4 and that of our saliva is 6.4. So blood is slightly basic and saliva is slightly
acidic.
Relation between pH and pOH
We know that Kw = [H+][OH-] = 10-14 at 298K
Taking negative logarithm on both sides:
-logKw = -log[H+] + -log[OH-] = -log 10-14
Or, pKw = pH + pOH = 14
Thus by knowing the pH, we can calculate pOH as pOH = 14 - pH
Ionisation constant of weak acids (Ka)
Consider a weak acid HX, which ionizes only partially as: HX + H2O H3O+ + X-
Let ‘c’ be the initial concentration of HX and ‘α’ is the degree (extent) of dissociation. (It is the ratio of
the number of moles of the electrolyte dissociated to the total number of moles).
Then, HX(aq) + H2O(l) ⇌ H3O+(aq) + X-(aq)
Initial concn. c 0 0
Eqm. concn. c(1-α) cα cα
[H3 O+ ][X− ]
The dissociation constant, Ka =
[HX]
Where Ka is the dissociation constant of the weak acid.
cα.cα 𝑐𝛼 2
Or, Ka = =
c(1−α) 1−𝛼
Larger the value of Ka, stronger is the acid. The negative logarithm of Ka is called pKa.
i.e. pKa = – logKa.
Greater the value of Ka, smaller will be the value of pKa and stronger will be the acid.
Ionisation constant of weak bases (Kb)
Consider a weak base MOH, which ionizes partially as: MOH ⇌ M+ + OH-
Let ‘c’ be the initial concentration of MOH and ‘α’ is the degree of dissociation.
Then, MOH(aq) + H2O(l) ⇌ M+(aq) + OH-(aq)
Initial concn. c 0 0
Eqm. concn. c(1-α) cα cα

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[M+ ][OH− ]
The dissociation constant of weak base, Kb = [MOH]
cα.cα 𝑐𝛼 2
Or, Kb = =
c(1−α) 1−𝛼
The negative logarithm of Kb is called pKb.
i.e. pKb = – logKb.
As the value of Kb increases, pKb decreases and the basic strength increases.
Relation between Ka, Kb and Kw
For conjugate acid – base pair Ka and Kb are related as: Ka x Kb = Kw
This can be deduced as follows:
[NH3 ][H3 O+ ]
NH4+ + H2O NH3 + H3O+; Ka =
[NH4+ ]

+
[NH+ −
4 ][OH ]
NH3 + H2O NH4 + OH-; Kb =
[NH3 ]
Net reaction : 2H2O H3O+ + OH-; Kw = [H3O+][OH-]

[NH3 ][H3 O+ ] [NH+ −

4 ][OH ]
Ka x K b = x = [H3O+][OH-] = Kw
[NH+
4] [NH3 ]

i.e. Ka x Kb = Kw = 10-14
or, pKa + pKb = pKw = 14
Factors Affecting Acid Strength
The extent of dissociation of an acid and its acidic strength depend on the strength
and polarity of the H-A bond. Weaker the H-A bond, more easily it dissociates to give H+ ion and
hence stronger is the acid. Also, greater the polarity of the H – A bond (when the electronegativity
difference between the atoms H and A increases) the more easily it dissociates and hence greater is the
acidity.
In a group, acidity is mainly determined by bond strength. From top to bottom in a group, as the
size of A increases, H-A bond strength decreases and so the acid strength increases. Thus acidic strength
of hydrohalic acids increases in the order: HF < HCl < HBr < HI.
In a period, acidity is mainly determined by polarity of the bond. As the electronegativity of A
increases from left to right in a period, the strength of the acid also increases. So the acidity of hydrides
of second period elements increases in the order: CH4 < NH3 < H2O < HF.
Hydrolysis of Salts and the pH of their Solutions
The interaction of anion or cation or both of a salt with water is known as salt
hydrolysis. The cations (e.g., Na+, K+, Ca2+, Ba2+, etc.) of strong bases and anions (e.g., Cl–, Br–, NO3 –,
ClO4– etc.) of strong acids do not get hydrolyse. So the solutions of salts formed from strong acids and
bases (e.g. NaCl, KCl, NaNO3, KNO3, Na2SO4, K2SO4 etc.) are neutral. i.e., their pH is 7.
1. Hydrolysis of salt of strong base and weak acid: Sodium acetate (CH3COONa), sodium carbonate
(Na2CO3), potassium cyanide (KCN) etc. are examples for such type of salts. Here only the anion of
the weak base undergoes hydrolysis (since cation of the strong base does not hydrolyse). So the
solution of such salts will be basic. i.e. pH > 7.
pH of such salt solution is given by pH = 7 + ½ (pKa + log C) where C is the concentration of salt.
2. Hydrolysis of salt of weak base and strong acid: NH4Cl, NH4NO3, CuSO4 etc. are examples for such
type of solutions. Here only cation of weak base undergoes hydrolysis. So the solution is acidic.
pH of such a solution is given by pH = 7 + ½ (pKb + log C).

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3. Hydrolysis of salt of weak base and weak acid: Ammonium acetate (CH3COONH4), ammonium
carbonate [(NH4)2CO3] etc. are examples for such type of salts. Here both cation and anion
undergo hydrolysis and hence weak acid and weak base are produced in solution. So the solution
may be neutral, acidic or basic depending upon the relative strength of acid and base formed.
pH of such a solution is given by pH = 7 + ½ (pKa + pKb).
Common Ion Effect
It is the suppression of the dissociation of a weak electrolyte by the addition of a
strong electrolyte containing a common ion.
For e.g. consider the dissociation of acetic acid (a weak electrolyte).
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
If we add some sodium acetate (CH3COONa) to the above equilibrium reaction, the
concentration of acetate ion increases. Then according to Le-Chatelier’s principle, the equilibrium will be
shifted towards left or, the rate of forward reaction decreases. i.e. the dissociation rate of acetic acid
decreases. This is known as common ion effect.
Another example is the dissociation of the weak base ammonium hydroxide (NH4OH)
NH4OH(aq) ⇌ NH4+(aq) + OH- (aq)
If we add some NH4Cl to the above equilibrium process, the concentration of NH4+ increases and hence
the equilibrium shifted to the left. i.e. the dissociation rate of NH4OH decreases.
Buffer Solutions
Solution which resists the change in pH on dilution or with the addition of small
amount of acid or alkali is called Buffer solution. There are two types of buffer solutions – acidic
buffer and basic buffer.
Acidic buffer is a mixture of a weak acid and its salt with a strong base. E.g. a mixture of acetic
acid and sodium acetate acts as an acidic buffer around pH 4.75.
Basic buffer is a mixture of a weak base and its salt with a strong acid. E.g. a mixture of NH 4OH
and NH4Cl acts as a basic buffer around pH 9.25.
PH of a Buffer solution – Henderson - Hasselbalch Equation
Consider an acidic buffer prepared by mixing a weak acid HA and its conjugate base A-. The weak acid HA
ionises in water as:
HA + H2O ⇌ H3O+ + A-
[𝐻3 𝑂+ ][𝐴− ]
The dissociation constant of weak acid, Ka =
[𝐻𝐴]
Taking –ve logarithm on both sides:
-log Ka = -log[H3O+] + - log[A-] – -log[HA]
Or, -log[H3O+] = -logKa + log[A-] – log[HA]
[A− ]
Or, pH = pKa + log
[HA]
This equation is known as Henderson-Hasselbalch equation.
[𝐒𝐚𝐥𝐭]
The equation can be written in general form as: pH = 𝐩𝐊 𝐚 + log
[𝐀𝐜𝐢𝐝]
[𝐒𝐚𝐥𝐭]
For a basic buffer, pOH = 𝐩𝐊𝐛 + log
[𝐁𝐚𝐬𝐞]
[𝐒𝐚𝐥𝐭]
or, pH = 14 – [𝐩𝐊𝐛 + 𝐥𝐨𝐠 ]
[𝐁𝐚𝐬𝐞]

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Solubility Equilibrium
The solubility of a salt in solvent mainly depends on the lattice enthalpy and
solvation enthalpy. As a general rule, for a salt to be able to dissolve in a particular solvent
its solvation enthalpy must be greater than its lattice enthalpy.
Each salt has its characteristic solubility which depends on temperature. We can classify salts on
the basis of their solubility in the following three categories.
Category I Soluble Solubility > 0.1M
Category II Slightly Soluble Solubility in between 0.01M and 0.1M
Category III Sparingly Soluble Solubility < 0.01M
Solubility Product Constant
Consider the dissociation of a sparingly soluble salt in water. Since it dissolves only partially,
there exists an equilibrium between the undissolved solid and the ions.
e.g. Solution of barium sulphate (BaSO4)
BaSO4 (s) Ba2+(aq) + SO42- (aq)
−
[Ba2+ ][SO2−
4 ]
The equilibrium constant, K =
[BaSO4 ]
For a pure solid, the concentration remains constant.
Therefore, K.[BaSO4] = [Ba2+][SO42-] Or, Ksp = [Ba2+][SO42-]
Where Ksp is called the solubility product constant or simply the solubility product. It is defined as the
product of the molar concentration of ions of a sparingly soluble salt or in a saturated solution.
If S is the molar solubility of BaSO4, then Ksp = S x S = S2
For a general salt AxBy, its dissociation can be denoted as:
AxBy(s) xAy+ (aq) + yBx- (aq); Ksp = [Ay+]x[Bx-]y
If the concentration in the above equation is not the equilibrium concentration, then K sp is given by Qsp.
At equilibrium, Ksp = Qsp.
If Ksp > Qsp, the dissolution process occurs and if Ksp < Qsp, the precipitation of the salt occurs.
Solubility product and common ion effect found application in the purification of NaCl. If we
take a saturated solution of NaCl and pass HCl gas through it, then NaCl gets precipitated due to the
increased concentration of Cl- ions. NaCl thus obtained has very high purity.
=====================================================================================
Q1) If the concentration of hydrogen ion in a soft drink is 3 x 10-3 M, calculate
its pH.
Ans: Here [H+] = 3 x 10-3
We know that pH = -log[H+]
= -log (3 x 10-3) = 2.523
Q2) Calculate the solubility (S) of CaSO4 at 298 K, if its solubility product constant
(Ksp) at this temperature is 9 x 10-6.
Ans: CaSO4 (s) ⇌ Ca2+(aq) + SO42- (aq)
KSP = S2. Here KSP = 9 x 10 -6
So, S = √KSP = √(9 x 10 -6) = 3 x 10 –3 M
Q3) Find the value of Kc for the following equilibrium if the value of Kp is 1.8 x 10-2 atm
at 600 K. (R= 0.0821 L atm K-1mol-1): 2NOCl(g) ⇌ 2NO(g) + Cl2(g)
Ans: Here Kp= 1.8 x 10-2, R = 0.0821 atm/K/mol
∆n = nP(g)-nR(g) = 3 - 2 = 1 and T = 600K

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Kp = Kc (RT)∆n
1.8 x 10-2 = Kc (0.0821 x 600)1
1.8 x 102
Kc = = 3.65 x 10-4
0.0821 x 600
Q4) Calculate the pH of a 0.01 M acetic acid solution with the degree of
ionization 0.045.
Ans: Degree of ionisation, α = 0.045
[H3O+] = cα = 0.01 x 0.045 = 4.5 x 10-4
pH = -log[H3O+] = -log (4.5 x 10-4) = 3.3468
Q5) Calculate the pH of an acidic buffer containing 0.1 M CH3COOH and 0.5 M
CH3COONa. [Ka for CH3COOH is 1.8 x 10-6].
[𝑠𝑎𝑙𝑡]
Ans: For an acidic buffer Henderson – Hasselbalch equation, pH = pKa + log [𝑎𝑐𝑖𝑑]
Here [acid] = 0.1M, [salt] = 0.5M and Ka = 1.8 x 10-6
pKa = -log Ka = - log(1.8 x 10-6) = 5.7447
[𝑠𝑎𝑙𝑡]
pH = pKa + log[𝑎𝑐𝑖𝑑]
[0.5]
= 5.7447 + log [0.1] = 6.444
Q6) The solubility of Mg(OH)2 at 298K is 1.5 x 10-4. Calculate the solubility
product.
Ans: Let the solubility of Mg(OH)2 is S. The dissociation of Mg(OH)2 can be represented as:
Mg(OH)2 (s) ⇌ Mg2+(aq) + 2 OH- (aq)
Eqm. Concn: S S 2S
KSP = [Mg ][OH ] = S x (2S)2
2+ - 2

i.e. KSP = 4S3

Here S= 1.5 x 10-4
So, KSP = 4 x (1.5 x 10-4)3 = 1.35 x 10-11
Q7) The ionization constant of nitrous acid is 4.5 x 10-4. Calculate the pH of 0.04
M solution of nitrous acid in water. (Hint: HNO2+ H2O ⇌ H3O+ + NO2– ; Ka = Cα2)
Ans: Ka = 4.5 x 10-4, C = 0.04M
Ka = Cα2
𝐾 4.5 𝑥 10−4
α = √ 𝐶𝑎 =√ 0.04
= 0.106
[H3O+] = cα = 0.04 x 0.106 = 0.00424
pH = -log[H3O+] = -log (0.00424) = 2.373
Q8) Calculate the pH of a 0.1 M solution of NaOH.
Ans: NaOH → Na+ + OH-
0.1 M 0.1 M

[OH-] = 0.1 M
pOH = - log[OH-] = -log (0.1) = 1
pH = 14 – pOH = 14 – 1 = 13
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

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7. REDOX REACTIONS
Redox reactions involve oxidation and reduction. The important concepts relating to redox
reactions are:
I. Classical Concept: According to this concept, oxidation is the process of addition of
oxygen/electronegative element to a substance or removal of hydrogen/electropositive
element from a substance.
Reduction is the process of removal of oxygen/electronegative element from a
substance or addition of hydrogen/electropositive element to a substance.
Substance which is oxidised is called reducing agent and the substance which is
reduced is called oxidising agent.
If oxidation and reduction take place simultaneously, the process is called Redox reaction.
i.e. Reduction + Oxidation → Redox reactions
E.g. Zn + CuO → ZnO + Cu
Here Zn is converted to ZnO. i.e oxygen is added to Zn. So it is oxidised and hence the reducing
agent. CuO is converted to Cu. i.e. oxygen is removed from Cu. So it is reduced and hence it is the
oxidising agent.
Other examples are:
1. FeCl3 + H2 → FeCl2 + 2HCl
Here the electronegative Cl atom is removed from FeCl3. So it is reduced. H2 is oxidised since an
electronegative Cl atom is added to it. FeCl3 is the oxidising agent and H2 is the reducing agent.
2. 2 H2S(g) + O2 (g) → 2 S (s) + 2 H2O (l)
Here H2S is oxidised and O2 is reduced.

II. Electronic Concept: According to this concept oxidation is the process of removal
(losing) of electron and reduction is the process of addition (gaining) of electron. A redox
reaction is the process of exchange of electrons between two or more substances.
A substance that accepts electron is called oxidising agent and a substance that donates electron is
called a reducing agent.
E.g. In the reaction Zn + Cu2+ → Zn2+ + Cu, Zn loses two electrons and forms Zn2+. So it is oxidised.
Cu gains two electrons and forms Cu. So it is reduced. Here Zn is the reducing agent and Cu 2+ is the
2+

oxidising agent.
Other examples are:
1. Reaction between Cu and Ag+

Here Cu loses two electrons. So it is oxidised and is the reducing agent. Ag+ accepts an electron.
So it is reduced and is the oxidising agent.
In the first example, Cu is reduced while in the second reaction it is oxidised. So the oxidation or
reduction of a metal depends on the nature of the metal to which it is combined.
The series in which the different metals are arranged in the decreasing order of their reactivity is
called electrochemical series or reactivity series. Generally, a metal lying above in the reactivity series
can displace another metal from its salt solution. For example Zn can displace copper from an aqueous
solution of copper sulphate, since Zn lies above Cu in the electrochemical series.

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2. Reaction between cobalt and nickel ion.

Here Co is oxidised to Co2+ and Ni2+ is reduced to Ni.

Oxidation number
Oxidation number of an element in a compound is the residual charge on the element when all
the other atoms are removed from it as ions.
For example oxidation number of Mn in KMnO4 is the residual charge on Mn when one K atom and four
O atoms removed from it as K+ and O2- ions respectively.
Rules used for the calculation of oxidation number
1. The oxidation number of all elements in the free or the uncombined state is zero. For e.g.
oxidation number of H2, O2, Cl2, O3, P4, S8, Na, Mg, Al etc. is zero.
2. For simple ions, the oxidation number is equal to the charge on the ion. Thus Na + ion has an
oxidation number of +1, Mg2+ ion +2, Fe3+ ion +3, Cl– ion –1, O2– ion –2 and so on.
3. All alkali metals have oxidation number of +1 and all alkaline earth metals have an oxidation
number of +2. Aluminium shows an oxidation number of +3 in all of its compounds.
4. The common oxidation number of oxygen is – 2. But in peroxides (like H2O2, Na2O2 etc.), oxidation
number of oxygen is – 1 and in superoxides (e.g., KO2, RbO2), it is – ½. In oxygen difluoride (OF2) and
dioxygen difluoride (O2F2), oxygen is assigned an oxidation number of +2 and +1 respectively.
5. The common oxidation number of hydrogen is +1. But it shows an oxidation number of -1 in metal
hydrides (like NaH, CaH2 etc.).
6. The common oxidation number of halogens is -1. Fluorine shows only -1 oxidation number in all of
its compounds. But other halogens show positive oxidation numbers also in their oxides and
oxoacids.
7. The algebraic sum of the oxidation numbers of all the atoms in a compound is zero.
8. In polyatomic ion, the sum of the oxidation numbers of all the atoms is equal to charge on the ion.
Stock Notations
Alfred Stock proposed some notations to represent the oxidation number of a metal in a compound.
According to this, the oxidation number is represented in Roman numeral in brackets after the symbol
of the metal in the molecular formula. Thus aurous chloride and auric chloride are written as Au(I)Cl and
Au(III)Cl3. Similarly, stannous chloride and stannic chloride are written as Sn(II)Cl2 and Sn(IV)Cl4. Stock
notation for MnO2 is Mn(IV)O2.
III. Oxidation number Concept: According to this concept, oxidation is the process of
increase in the oxidation number of an element and reduction is the process of decrease in
the oxidation number of an element.
A reagent that can increase the oxidation number of an element in a given
substance is called oxidising agent or oxidant and a reagent which lowers the oxidation
number of an element in a given substance is called reducing agent or reductant. A redox
reaction is a reaction which involves change in oxidation number of the interacting species.
E.g. in the reaction

,
the oxidation number of Zn increases from 0 to +2 and that of Cu in CuSO4 decreases from +2 to 0. So Zn
is oxidised and Cu in CuSO4 is reduced.

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In the reaction:

,
the oxidation number of Cr decreases from +3 to 0. So it is reduced and is the oxidising agent. The
oxidation number of Al increases from 0 to +3. So it is oxidised and is the reducing agent.
Types of redox reactions
1. Combination reactions: A combination reaction may be denoted as A + B → C
Here either A or B or both A and B must be in the elemental form. All combustion reactions are
combination redox reactions, since here one of the reactants is O2. Examples are:

2. Decomposition reactions:
Decomposition reactions are the opposite of combination reactions. It involves the breakdown
of a compound into two or more components, in which at least one must be in the elemental state. It
may be denoted as: C → A + B. Examples are:

All decomposition reactions are not redox reactions. For example, decomposition of calcium
carbonate is not a redox reaction, since it does not involve any change in the oxidation number.

3. Displacement reactions: Here an ion (or an atom) in a compound is replaced by an ion (or an
atom) of another element. It may be denoted as: X + YZ → XZ + Y
Displacement reactions are divided into two - metal displacement and non-metal displacement.
a) Metal displacement reactions: Here a metal in a compound is displaced by another metal in the
uncombined state. These reactions find many applications in metallurgical processes in which pure
metals are obtained from their compounds in ores. Some examples are:

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b) Non-metal displacement reactions: The non-metal displacement redox reactions mainly include
hydrogen displacement. All alkali metals and some alkaline earth metals (Ca, Sr, and Ba) will displace
hydrogen from cold water. Less active metals such as magnesium and iron react with steam and
produce hydrogen gas.

Most of the metals react with acids and liberate Hydrogen.

Other examples of non-metal displacement reactions are:

Fluorine can displace O2 from water. Chlorine can displace bromine and iodide from their aqueous salt
solutions.

4. Disproportionation reactions:
These are a special type of redox reaction. In a disproportionation reaction, an
element in one oxidation state is simultaneously oxidised and reduced. One of the reacting
substances always contains an element that can exist in at least three oxidation states. The element in
the reactant is in the intermediate oxidation state and both higher and lower oxidation states of that
element are formed in the reaction.
E.g. The decomposition of hydrogen peroxide.

Here the oxygen of peroxide is in –1 state and it is converted to zero oxidation state in O2 and –2
oxidation state in H2O.

Another example is:

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Balancing of Redox Reactions

There are two methods for balancing a redox reaction – Oxidation number method and half reaction
method.
1. Oxidation Number Method: This method involves the following steps:
Step 1: Write the correct formula for each reactant and product.
Step 2: Assign the oxidation number of each element and identify the atoms which undergo change in
oxidation number.
Step 3: Calculate the change in oxidation number per atom and equate them by multiplying with
suitable coefficients.
Step 4: Balance all the atoms except oxygen and hydrogen.
Step 5: Now equate the ionic charges on both sides of the equation by adding H+ or OH– ions on the
appropriate side. If the reaction is carried out in acidic solution, use H+ ions in the equation; if in basic
solution, use OH– ions.
Step 6: Make the numbers of hydrogen atoms in the expression on the two sides equal by adding water
(H2O) molecules to the reactants or products. Now, also check the number of oxygen atoms.

Q1) Balance the following Redox equation by oxidation number method :

P4(s) + OH-(aq) → PH3(g) + HPO2- (aq)
Ans:
Step 1: Write the skeletal equation. P4 + OH – PH3 + HPO2 –
Step 2: Assign the oxidation number of each element and identify the atoms which undergo
change in oxidation number.
0 0 -3 +2
P4 + P4 +OH – PH3 + HPO2 –
Step 3: Calculate the change in oxidation number per atom and equate them by multiplying with
suitable coefficients.

O.N decreased by 3
0 0 -3 +2
P4 + P4 +OH – PH3 + HPO2 –
O.N increased by 2

2P4 + 3P4 +OH – PH3 + HPO2–

Step 4: Balance all the atoms except oxygen and hydrogen.
2P4 + 3P4 +OH – 8 PH3 + 12 HPO2–
Step 5: Now equate the ionic charges on both sides. Since the reaction occurs in in basic medium,
add 11 OH– ions on LHS.
2P4 + 3P4 +OH – + 11OH– 8 PH3 + 12 HPO2-
Step 6: Now balance the hydrogen atoms by adding 12 water (H2O) molecules on LHS.
5P4 + 12OH– + 12H2O 8 PH3 + 12 HPO2-
Now the equation becomes balanced.
2. Half reaction method: In this method, the equation is divided into 2 half reactions –
oxidation half reaction and reduction half reaction. They are balanced separately and then added
together to get the net balanced equation. The different steps involved in this method are:
Step 1: Produce unbalanced equation for the reaction in ionic form. Assign the oxidation number of
each element and find out the substance oxidised and reduced.

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Step 2: Separate the equation into half reactions - oxidation half reaction and reduction half reaction.
Step 3: Balance the atoms other than O and H in each half reaction individually.
Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and H+ to balance H
atoms. In basic medium also add equal number of OH- ions on both sides of the equation.
Step 5: Now balance the ionic charges. For this add electrons to one side of the half reaction. Make the
number of electrons equal in the two half reactions by multiplying one or both half reactions by
appropriate coefficients.
Step 6: Now add the two half reactions to get the overall reaction and cancel the electrons on each side.
Step 7: Verify that the equation contains the same type and number of atoms and the same charges on
both sides.
Q2) Balance the following Redox equation by ion-electron method (Half reaction method)
Cl2O7 + H2O2 → ClO2 - + O2 + H+
Ans: Step-1: Assign the oxidation number of each element and find out the substance oxidised
and reduced.
+7 -2 +1 -1 +3 -2 0 +1
Cl2O7 + H2O2 ClO2 - + O2 + H+
Here the oxidation number of O is increased and that of Cl is decreased. So O in H2O2 is oxidised
and Cl in Cl2O7 is reduced.
Step-2: Separate the equation into 2 half reactions -oxidation half reaction and reduction half
reaction.
Oxidation half: H2O2 O2 Reduction half: Cl2O7 ClO2–
Step-3: Balance the atoms other than O and H in each half reaction individually.
Oxidation half: H2O2 O2 Reduction half: Cl2O7 2 ClO2–
Step-4: Now balance O and H atoms. Add H2O to balance O atoms and H+ to balance H atoms
since the reaction occurs in acidic medium.
Oxidation half: H2O2 O2 + 2 H+ Reduction half: Cl2O7 + 6 H+ 2 ClO2– + 3 H2O
Step -5: Now balance the ionic charges. For this add electrons to one side of the half reaction.
Oxidation half: H2O2 O2 + 2 H+ + 2e- Reduction half: Cl2O7 + 6 H++ 8e- 2 ClO2– + 3
H2O
Step-6: Now add the two half reactions after equating the electrons.
Oxidation half: (H2O2 O2 + 2 H+ + 2e- ) x 4
Reduction half: (Cl2O7 + 6 H++ 8e- 2 ClO2– + 3 H2O) x 1
Overall reaction is: 4 H2O2 + Cl2O7 4 O2 + 2 H+ + 2 ClO2– + 3 H2O
Now the equation is balanced.
REDOX REACTIONS AND ELECTRODE PROCESSES
Redox reactions find applications in electrode processes in electrochemical cells. An
electrochemical cell (Galvanic cell) is a device that converts chemical energy of a redox reaction to
electrical energy. Any electrochemical cell contains two electrodes
– anode and cathode. The electrode at which oxidation takes place
is the anode and the other electrode at which reduction occurs is
the cathode.
An example for electrochemical is Daniel cell. It contains a Zn rode
dipped in ZnSO4 solution and Copper rode dipped in CuSO4 solution.
The two solutions are connected externally by a metallic wire
through a voltmeter and a switch and internally by a salt bridge.
The reaction taking place in a Daniel cell is:
Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
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This reaction is a combination of two half reactions:

(i) Cu2+(aq) + 2e- → Cu(s) (reduction half reaction)
(ii) Zn(s) → Zn (aq) + 2e- (oxidation half reaction)
2+

The reduction half reaction occurs on the copper electrode while the oxidation half reaction
occurs on the zinc electrode. These two portions of the cell are also called half-cells or redox couples.
The copper electrode may be called the reduction half-cell or cathode and the zinc electrode, the
oxidation half-cell or anode.
The flow of current is possible only if there is a potential difference between the copper
electrode and zinc electrode. The potential associated with each electrode is known as electrode
potential. It is the tendency of the electrode to lose or gain electron.
When the concentration of the electrolyte is unity and if the reaction is carried out at 298K, the
potential is called the Standard Electrode Potential (E0). By convention, the standard electrode potential
of hydrogen electrode (H+/H2 couple) is 0.00 volts. A negative E means that the redox couple is a
stronger reducing agent than the H+/H2 couple. A positive E means that the redox couple is a weaker
reducing agent than the H+/H2 couple.
********************************************************************************************
Q1) In an experiment a copper rod is dipped in AgNO3 solution. What happens to the
colour of the solution and why? Identify the oxidizing and reducing agents in this
reaction.
Ans: The solution becomes pale blue in colour. This is because Cu displaces Ag from AgNO3 solution.
Cu + 2AgNO3 → Cu(NO3)2 + 2Ag
Oxidizing agent is AgNO3 and reducing agent is Cu
Q2) Justify that the following reaction is a redox reaction:
H2S(g) + Cl2(g) → 2HCl (g) + S(s)
Ans: +1 -2 0 +1 -1 0
H2S(g) + Cl2(g) → 2HCl (g) + S(s)
Here the oxidation number of sulphur is increased (oxidation) and that of chlorine is decreased
(reduction). So, it is a redox reaction.
Q3) In a reaction 2Cu2O + Cu2S → 6Cu + SO2. Identify oxidizing agent and reducing
agent.
Ans: +1 -2 +1 -2 0 +4 -2
(ii) 2Cu2O + Cu2S → 6 Cu + SO2
Here the oxidation number of Cu in both Cu2O and Cu2S is decreased from +1 to 0. So, Cu is reduced
and it is the oxidizing agent. While the oxidation number of S is increased from -2 to +4. So, S in
Cu2S is oxidized and hence it is the reducing agent.
Q4) Check whether the reaction 2H2O2(l) → 2H2O(l) + O2(g) is a disproportionation
reaction. Justify your answer.
Ans: -1 -2 0
2H2O2(l) 2H2O(l) + O2(g)
Here the oxidation number of oxygen is simultaneously increased and decreased. So, it is a
disproportionation reaction.
Q5) Calculate the oxidation number of Cr in K2Cr2O7.
Ans: Let the oxidation number of Cr be x
Then 2 x (+1) + 2x + 7 x (-2) = 0
+2 + 2x + (-14) = 0
2x – 12 = 0 OR, X = 12/2 = 6
i.e., Oxidation number of Cr = +6
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8. ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES

AND TECHNIQUES
Organic chemistry is the branch of chemistry that deals with carbon compounds. But all carbon
compounds are not considered as organic compounds. (E.g. CO2, CO, metal carbonates, bicarbonates
etc.). So organic chemistry can be defined as the branch of chemistry that deals with
hydrocarbons and their derivatives. Hydrocarbons are the major class of organic compounds and
they contain only carbon and hydrogen atoms. All other organic compounds are formed by replacing
one or more hydrogen atoms of hydrocarbons by other atoms or groups (They are called hydrocarbon
derivatives).
All carbon compounds present in plants and animals are organic compounds. E.g. carbohydrates,
proteins, vitamins, nucleic acids, amino acids, fats and oils, natural polymers etc. Petroleum and coal are
the major source of organic compounds (hydrocarbons).
In ancient times, it was believed that a vital force (living body) is necessary for the production of
an organic compound. But in 1828, Frederic Wohler prepared urea in the laboratory, by heating
ammonium cyanate (NH4CNO). It was the first organic compound prepared in the laboratory.
Heat
NH4CNO → NH2CONH2
Ammonium cyanate Urea
Another scientist Kolbe synthesized acetic acid and Berthelot synthesized methane in the
laboratory. Nowadays about 95% of the organic compounds are synthesized in the laboratory.
Chemistry behind the existence of large number Carbon compounds
Carbon is a unique element and it can form large number of compounds due to the following reasons:
i) Tetravalency of carbon: In all of its compounds, the valency of carbon is four. Carbon has 4
electrons in its valency shell and requires 4 more electrons to complete the octet. So it attains the
octet configuration by forming 4 covalent bonds.
ii) Ability to form single bond and multiple bonds: C can form single bond and multiple bond (double
or triple bond) with itself and also with other elements like oxygen, nitrogen etc. This is possible by
sp3, sp2 or sp hybridisation.
iii) Catenation: Carbon shows catenation. It is the self-linking property of an element to form long
chains and rings.
iv) Isomerism: Carbon compounds can show isomerism. It is the phenomenon in which compounds
having same molecular formula but different structural formula or spatial arrangement of atoms.
Structural representation of organic compounds
An organic compound can be represented by the following ways:
1. Complete structural formula: Here all the bonds between atoms are denoted by dashes (----). A
single dash represents a single bond, a double dash represents a double bond and a triple dash
represents a triple bond. E.g.

2. Condensed stuctural formula: Here the carbon-hydrogen bonds or all the bonds are omitted
except the multiple bonds. It is a simplified representation of an organic compound.
E.g. ethane - CH3CH3, propane - CH3CH2CH3, butane - CH3CH2CH2CH3, ethene - CH2=CH2 etc.
The condensed formula can again simplified as follows:

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Butane – CH3(CH2)2CH3, Hexane- CH3(CH2)4CH3, Decane – CH3(CH2)8CH3 etc.

3. Bond line representation: It is the simplest form of representation of an organic compound.
Here carbon and hydrogen atoms are not shown and the lines representing carbon-carbon bonds are
drawn in a zig-zag fashion. The only atoms specifically written are oxygen, chlorine, nitrogen etc. The
free terminals denote methyl (–CH3) groups.
E.g. butane:

3-methyl pentane:

Heptanal: H

O
3-Methyl pentanoic acid: OH

O
4. Three-Dimensional Representation (Wedge Representation): Here the structure of an organic
molecule can be represented by using solid ( ) and dashed ( ) wedges. The solid-
wedge is used to indicate a bond projecting out of the plane of paper, towards the observer. The
dashed-wedge indicates the bond projecting out of the plane of the paper and away from the
observer. The broad end of the wedge is always towards the observer. The bonds lying in plane
of the paper are depicted by using a normal line (—).
E.g. methane

Classification of Organic compounds

Organic compounds can be broadly classified into two – Acyclic or open chain compounds and cyclic
or ring compounds.
1. Acyclic or open chain or aliphatic compounds: In these compounds, the carbon atoms are joined
together to form long chains which may be straight chain or branched chain. They are further
classified as saturated compounds and unsaturated compounds. Saturated compounds contain only
carbon – carbon single bonds. But unsaturated compounds contain atleast one carbon – carbon
multiple bond (double or triple bond. Saturated hydrocarbons are called alkanes and unsaturated
hydrocarbons are of two types – alkenes and alkynes.
2. Cyclic or closed chain or ring compounds: In these compounds, the carbon atoms are joined
together to form rings. These rings may be homocyclic or heterocyclic. If the ring contains only
carbon atoms, it is called homocyclic compound and if it contains atoms other than carbon (like O,
N, S etc), it is called heterocyclic compound.

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Homocyclic compounds are further classified into two – Alicyclic compounds and Aromatic
compounds. Alicyclic compounds contain atleast one carbo-cyclic ring. Alicyclic hydrocarbons are of
three types – cycloalkanes, cycloalkenes and cycloalkynes. Aromatic compounds are some special type
of compounds. These are of two types. Aromatic compounds containing benzene ring are called
benzenoid compounds and those which do not contain benzene ring are called non-benzenoid
compounds. E.g. for a non-benzenoid aromatic compound is tropolone.
Heterocyclic compounds may be alicyclic heterocyclic compounds or aromatic heterocyclic compounds.
The classification of organic compounds can be diagrammatically represented as follows:

Organic compounds

Acyclic or open chain or Cyclic or ring or

Aliphatic compounds closed chain compounds

Saturated Unsaturated Homocyclic Heterocyclic

compounds compounds compounds compounds

Alicyclic Aromatic Alicyclic Aromatic

Benzenoid Non-benzenoid

Functional groups: Atoms or group of atoms (except hydrogen) which are bonded to
carbon atoms are called functional groups. These groups are responsible for the characteristic
chemical properties of the organic compounds. Some important functional groups, their names and
name of the compounds are listed below:
Functional group Name of the group Name of compound
-OH Hydroxyl group Alcohol
-NH2 Amino group Amine
-X Halo group Halo compound
-CHO Aldehydric (formyl) group Aldehyde
-CO- or >CO Carbonyl (keto) group Ketone
-COOH Carboxyl group Carboxylic acid
-O- Oxy group Ether
-CN Cyano group Nitrile
-NO2 Nitro group Nitro compound

Homologous series: A series or group of organic compounds in which adjacent members

are differed by a –CH2 group is called a homologous series. The members of a homologous
series are called homologues. They contain same functional groups. So they have similar chemical
properties and show gradation in physical properties. They can be prepared by some general methods
of preparation. E.g. for homologous series are alkanes, alkenes, alkynes, alcohols, ethers, carboxylic
acids, aldehydes, ketones, amines, halo compounds etc.
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Nomenclature of organic compounds

An organic compound has two types of names – Common name and IUPAC name. The common
name is based on the source or some properties. For e.g. citric acid is named so because it is found in
citrus fruits and the acid found in red ant is named formic acid since the Latin word for ant is formica.
IUPAC Nomenclature of organic compounds
A systematic name of an organic compound is generally derived by identifying the parent
hydrocarbon and the functional group(s) attached to it. This name is called IUPAC name. It contains two
parts – word root and suffix or prefix. The word root indicates the number of carbon atoms in the
compound. The word roots for compounds containing 1 -12 carbon atoms are as follows:
No. of C atoms Word root No. of C atoms Word root
C1 Meth- C7 Hept-
C2 Eth- C8 Oct-
C3 Prop- C9 Non-
C4 But- C10 Dec-
C5 Pent- C11 Undec-
C6 Hex- C12 Dodec-

There are two types of suffixes – primary suffix and secondary suffix. Primary suffix indicates saturation
or unsaturation [for alkane the primary suffix is –ane, alkene –ene and for alkyne –yne]. Secondary suffix
indicates the type of functional group. Some functional groups are also indicated as prefixes.

Nomenclature of branched chain alkanes:

A branch (side chain or substituent) is obtained by removing a hydrogen atom from an alkane.
The resulting group is called an alkyl group [alkane – H = alkyl (i.e. word root + yl)]. The names of some
common branches are as follows:
Branch Name
-CH3 Methyl
-CH2-CH3 Ethyl
-CH2-CH2-CH3 n-propyl (normal propyl)
(CH3)2CH- Isopropyl
-CH2-CH2-CH2-CH3 n-butyl
CH3-CH-CH2-CH3 sec-butyl (secondary butyl)
(CH3)2CH-CH2- Isobutyl
(CH3)3C- tert-butyl (tertiary butyl)
(CH3)3C-CH2- Neopentyl

Rules for naming branched chain alkanes:

IUPAC recommenced the following rules for naming a branched chain alkane.
1. Select the longest continuous chain of carbon atoms. This chain is called parent chain or root chain.
If there is more than one such chain, the chain that contains maximum number of branches is
selected as the parent chain. Also identify all the branches or substituents.

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2. Number the carbon atoms of the parent chain in such a way that the branched carbon atoms get
the lowest possible numbers.
3. The names of alkyl groups attached as branches are then prefixed to the name of the parent alkane
and position of the substituents is indicated by the appropriate numbers.
4. If different alkyl groups are present, they are listed in alphabetical order. In alphabetical order, the
prefixes iso- and neo- are considered to be the part of the fundamental name of alkyl group. The
prefixes sec- and tert- are not considered to be the part of the fundamental name.
5. If two or more identical substituent groups are present then their numbers are indicated by prefixes
like di (for 2), tri (for 3), tetra (for 4), penta (for 5) etc and the numbers are separated by commas.
The number and word are separated by a hyphen. (The IUPAC name is written as a single word).
For example:

3-Ethyl-4,4-dimethylheptane

6. If the two substituents are found in equivalent positions, the lower number is given to the one
coming first in the alphabetical listing.
For example:

The above compound is 3-ethyl-6-methyloctane and not 6-ethyl-3-methyloctane.

7. While naming the branched alkyl groups, the carbon atom of the branch that attaches to the root
alkane is numbered 1.
For example:

1,3-dimethyl butyl-

IUPAC nomenclature of compounds containing functional groups

For naming organic compounds containing functional group, the following rules are used:
1. Select the longest continuous chain containing the functional group.
2. Number the carbon atoms in such a way that the carbon to which the functional group is attached
should get the lowest possible number. In the case of functional groups containing carbon atom like
–CHO, -CN, -COOH, -CONH2, -COX. -COOR etc. the numbering should start from the carbon atom of
the functional group. (i.e. carbon atom of these groups should be numbered as 1). (But for ketones,
the functional group –CO- should get the lowest possible number).
3. The name of the functional group is indicated by the following suffix or prefix.

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Functional Name of Suffix/Prefix IUPAC name

group compound
-OH Alcohol -ol Alkanol
-NH2 Amine -amine Alkanamine
-X Halo compound Halo- Haloalkane
-CHO Aldehyde -al Alkanal
>CO Ketone -one Alkanone
-COOH Carboxylic acid -oic acid Alkanoic acid
-O- Ether Alkoxy- Alkoxyalkane
-CN Nitrile -nitrile Alkanenitrile
-NO2 Nitro Nitro- Nitroalkane
compound
-C=C- Alkene -ene Alkene
-C≡C- Alkyne -yne Alkyne
-COOR Ester -oate Alkyl alkanoate
-CONH2 Acid amide -amide Alkanamide
-COX Acid halide -oyl halide Alkanoyl halide
-SO3H Sulphonic acid -sulphonic Alkanesulphonic
acid acid
In the case of suffixes, the ending –e of the corresponding alkane is replaced. E.g. IUPAC name
of the alcohol CH3-OH is methanol (methane + ol). But for nitriles, the –e of the corresponding
alkane is retained. E.g. IUPAC name of CH3-CH2-CN is propanenitrile.
In the case of alkenes and alkynes, the suffix –ane of the alkane is replaced by –ene and –yne
respectively. (i.e. word root + ene or yne). For naming alkenes or alkynes, the numbering is done in
such a way that the double or triple bond should get the lowest possible number.
Some examples are:
Compound IUPAC Name
CH3-CH2-CH=CH2 But-1-ene OR 1-Butene
CH3-CH=CH-CH3 But-2-ene OR 2-Butene
CH3-CH2-C≡C-CH3 Pent-2-yne OR 2-Pentyne
CH3-CH2-CH2-CH2-CH2-C≡CH Hept-1-yne OR 1-Heptyne
CH3-CH2-OH Ethanol
CH3-CH2-CHOH-CH2-CH2-CH3 Hexan-3-ol OR 3-Hexanol
CH3-CH2-CH2-CHO Butan-1-al or Butanal
HCHO Methanal
CH3-CO-CH3 Propanone
CH3-CO-CH2-CH2-CH3 Pentan-2-one OR 2-Pentanone
CH3-CH2-CH2-CO-CH2-CH2-CH2-CH3 Octan-4-one OR 4-Octanone
HCOOH Methanoic acid
CH3-COOH Ethanoic acid
CH3-CH2-CH2-COOH Butan-1-oic acid OR Butanoic acid

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CH3-CH2-Cl Chloroethane
CH3-CH2-CHBr-CH3 2-Bromobutane
CH2Cl-CH2-CH2-CH2-CH3 1-Chloropentane
CH3-CH2-CH2-NO2 1-Nitropropane
CH3-CH2-CH2-CN Butanenitrile
CH3-CH2-CH2-CH2-CH2-CN Hexanenitrile
CH3-O-CH3 Methoxymethane
CH3-CH2-O-CH3 Methoxyethane
CH3-CH2-CH2-O-CH2-CH3 1-Ethoxypropane
CH3-CH2-NH2 Ethanamine
CH3-CH2-CH(NH2)-CH3 Butan-2-amine OR 2-Butanamine
CH3-CH2-COOCH3 Methylpropanoate
CH3-CH2-COOCH2-CH3 Ethylpropanoate
CH3-CH2-COCl Propanoylchloride
CH3-CH2-CH2-CH2-COBr Pentanoylbromide
CH3-CH2-CH2-CONH2 Butanamide
CH3-CONH2 Ethanamide

Nomenclature of organic compounds containing more than one functional groups (Poly
functional compounds)
Here one of the functional groups is chosen as the principal functional group and the compound
is named on that basis. The remaining functional groups (called subordinate functional groups) are
named as substituents using the appropriate prefixes. The choice of principal functional group is made
on the basis of order of preference. The decreasing order of priority for some functional groups is
-COOH, –SO3H, -COOR, -COCl, -CONH2, -CN,-CHO, >CO, -OH, -NH2, >C=C<, -C≡C-
The groups like alkyl (–R), phenyl (C6H5-), halogens (F, Cl, Br, I), nitro (–NO2), alkoxy (–OR) etc. are always
prefix substituents.
For example if a compound contains both alcoholic and aldehydic groups, it is named as
hydroxyalkanal, since here aldehydic group is the principal functional group and –OH group is the
subordinate functional group.
The prefix names of some functional groups are as follows:
Functional group Prefix name
-OH Hydroxyl-
-NH2 Amino-
-X Halo-
-CHO Formyl-
>CO Oxo-
-COOH Carboxy-
-O- Alkoxy-
-CN Cyano-
-NO2 Nitro-
-COOR Alkoxy carbonyl-
-CONH2 Carbamoyl-
-COX Halocarbonyl-

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While numbering the carbon chain, the principal functional group should get the lowest possible
number.
Some examples are:
Compound IUPAC Name
CH3-CHOH-CH2-CO-CH3 4-Hydroxy-2-pentanone
CH2Cl-CH2-CHBr- CH2-CH2OH 3-Bromo-5-chloropentan-1-ol or, 3-Bromo-5-chloro-1-pentanol
CH3-CH2-CO-CH2-CH2-CHO 4-Oxohexanal
CH3-CHNH2-CH2-COOH 3-Aminobutanoic acid
CH3-CH2-CHCl-CH2-CO-CH2-COOH 5-Chloro-3-oxo-heptanoic acid

If a compound contains more than one same functional group, their number is indicated by
adding the numeral prefixes di, tri, etc. before the suffix. In such cases the full name of the parent alkane
is written before the suffix. However, the ending – ne of the parent alkane is dropped in the case of
compounds having more than one double or triple bonds.
When both double and triple bonds are present, the double bonds are given the lowest numbers.
Here first give the suffix of the double bond (-ene) and then that of the triple bond (-yne) [the ending –e
of the suffix –ene is avoided].
Examples:
Compound IUPAC Name
CH2OH-CH2OH Ethane-1,2-diol (Ethylene glycol)
CH2OH-CHOH-CH2OH Propane-1,2,3-triol (Glycerol)
CHO-CHO Ethane-1,2-dial (Glyoxal)
COOH-COOH Ethane-1,2-dioic acid (Oxalic acid)
CH3-CO-CH2-CO-CH3 Pentane-2,4-dione
CH2=CH-CH=CH2 1,3-Butadiene or Buta-1,3-diene
CH≡C-CH2-C≡CH 1,4-Pentadiene or Penta-1,4-diene
CH2=CH-CH2-C≡ CH Pent-1-en-4-yne
CH≡C-CH=CH-C=CH2 Hexa-1,3-dien-5-yne
(The names given in the bracket are the common names)
Nomenclature of Substituted Benzene Compounds
For IUPAC nomenclature of substituted benzene compounds, the substituent is placed as prefix to
the word benzene. But common names of some compounds are accepted by IUPAC

Nomenclatrue of di or polysubstituted benzene

If benzene ring is disubstituted, the position of substituents is indicated by numbering the carbon
atoms of the ring such that the substituents get the lowest possible numbers.
Example – Dibromobenzene

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In the common system of nomenclature the terms ortho (o), meta (m) and para (p) are used as
prefixes to indicate the relative positions 1,2- 1,3- and 1,4- respectively. So 1,2-dibromobenzene is
named as ortho-dibromobenzene (o-dibromobenzene), 1,3-dibromobenzene as meta-dibromobenzene
(m-dibromobenzene) and 1,4-dibromobenzene as para-dibromobenzene (p-dibromobenzene).
For tri - or higher substituted benzene derivatives, these prefixes cannot be used and the
compounds are named by identifying substituent positions on the ring by following the lowest locant
rule. In some cases, common name of benzene derivatives is taken as the base compound. Substituent
of the base compound is assigned number1 and then the direction of numbering is chosen such that the
next substituent gets the lowest number. The substituents are named in alphabetical order.
Some examples are:

When a benzene ring is attached to an alkane with a functional group, it is considered as substituent,
instead of a parent. The name for benzene as substituent is phenyl (C6H5-, also abbreviated as Ph).
Example:

Isomerism
The phenomenon of existence of two or more compounds having the same molecular
formula but different structural formula or spatial arrangement of atoms is known as
isomerism. Such compounds are called as isomers. Isomers have different physical and chemical
properties. Isomerism can be broadly classified into two –structural isomerism and stereo isomerism.
1. Structural isomerism
Compounds having same molecular formula but different structural formula (arrangement of atoms) are
called structural isomers and the phenomenon is called structural isomerism. There are mainly four
types of structural isomerism:
a) Chain Isomerism: Isomers differ in carbon chain or skeleton are called chain isomers and the
phenomenon is called chain isomerism.
E.g.: Pentane (C5H12)
CH3-CH2-CH2-CH2-CH3 CH3-CH-CH2-CH3 CH3
n-pentane
CH3 CH3 C CH3

isopentane CH3
(2-Methylbutane) neopentane (2,2-Dimethylpropane)
b) Position isomerism: Isomers which differ in the position of the substituent or side chain are
called position isomers and the phenomenon is called position isomerism.
E.g. : Alcohol with molecular formula C4H10O may be 1-butanol or 2-butanol
CH3-CH2-CH2-CH2-OH CH3-CHOH-CH2-CH3
1-Butanol 2-Butanol
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c) Functional group isomerism: Isomers which differ in the functional group are called functional
group isomers and the phenomenon is called functional group isomerism. This isomerism is
shown by alcohols and ethers and aldehydes and ketones.
E.g. compound with the molecular formula C2H6O may be an alcohol ethanol (CH3-CH2OH) or an
ether methoxy methane (CH3-O-CH3).
d) Metamerism: Isomers which differ in the carbon chain (alkyl groups) around the functional group
are called metamers and the phenomenon is called metamerism. It is commonly shown by
ethers.
E.g.: Ether with molecular formula C5H12O may be methoxybutane (CH3-O-CH2-CH2-CH2-CH3) or
ethoxypropane (CH3-CH2-O-CH2-CH2-CH3).
2. Stereo isomerism
Compounds having same molecular formula but different spatial arrangement of atoms
are called stereoisomers and the phenomenon is called stereoisomerism. They have same atom
to atom bond. There are two types of stereo isomerism – Geometrical isomerism and Optical
isomerism.
The diagrammatic representation of different types of isomerism is:

ORGANIC REACTION MECHANISM - Fundamental Concepts

In an organic reaction, the organic molecule (called substrate) reacts with an attacking reagent to
form one or more intermediates and finally the products.
Substrate + attacking reagent → Intermediate → Products
A sequential account of different steps in which the reactants are converted to products is called
reaction mechanism.
Fission of a covalent bond
A covalent bond can be broken either by homolysis or by heterolysis.
1. Homolysis:
It is a type of bond fission in which each of the bonded atoms gets one of the electrons of the shared
pair. Here the movement of a single electron takes place. The single electron movement is shown by
half – headed arrow or fish hook arrow ( ).

The species formed as a result of homolysis is called free radical. These are species which contain
an odd electron or an unpaired electron.

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There are three types of free radicals – primary (10), secondary (20) and tertiary
(30). Their stability increases in the order 10 < 20 < 30.

Organic reactions, which take place by homolytic fission are called free radical or homopolar or
nonpolar reactions.
2. Heterolysis:
It is a type of bond fission in which the shared pair of electrons remains with one of the fragments.
After heterolysis, one atom has a sextet of electron and a positive charge and the other atom has
an octet of electron with atleast one lone pair and a negative charge.
For example the bond cleavage in methyl bromide takes place in the following manner.

A species having a carbon atom possessing sextet of electrons and a positive charge is called a
carbocation (carbonium ion). They are of three types – primary, secondary and tertiary.
Carbocations are highly unstable and reactive species. Their stability increases in the
order 10 < 20 < 30. The high stability of tertiary carbocations is due to inductive effect and hyper
conjugation. In carbocations, carbon atom is in sp2 hybridisation and hence they have trigonal planar
(planar triangular) shape.
If the group attached to the carbon atom is less electronegative than C, due to heterolytic
cleavage, a species with C atom containing a shared pair of electrons and negative charge is formed.

Such a species carrying a negative charge on carbon atom is called carbanion. They are also
unstable and reactive. Their stability increases in the order : 30 < 20 < 10.
The organic reactions which proceed through heterolytic bond cleavage are called ionic or
heteropolar or polar reactions.
Differences between Homolysis and Heterolysis
Homolytic bond cleavage (Homolysis) Heterolytic bond cleavage (Heterolysis)
It is a type of bond fission in which each of Here, the bond breaks in such a manner that
the bonded atoms gets one of the electrons the shared pair of electrons remains with
of the shared pair. one of the fragments.
Movement of a single electron occurs. Movement of a pair of electrons occurs.
The species formed as a result of homolysis The species formed as a result of
is called free radical. heterolysis, may be carbocations or
carbanions.

Substrate and Reagent

A molecule whose carbon is involved in new bond formation is called substrate and the other molecule or
species is called reagent. When both of the reactants contain carbon atoms, the molecule under
observation is the substrate.
E.g. CH2 = CH2 + Br2 CH2Br – CH2Br
Substrate Reagent Product

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Nucleophiles and Electrophiles

A reagent that brings an electron pair is called a nucleophile (:Nu –) and the reaction
is called nucleophilic reaction. Or, nucleophiles are electron rich species attack at electron
deficient centre. (The word nucleophile means nucleus seeking).
Examples for nucleophiles are OH-, CN-, NO2-, Cl-, Br-, I-, H2O, NH3, R-NH2 etc.
A reagent that takes away an electron pair is called an electrophile (E+) and the
reaction is called electrophilic reaction. Or, electrophiles are electron deficient species
attack at electron rich centre. (The word electrophile means electron seeking).
Examples for electrophiles are carbocations (R+), -CHO, >CO, X+ (halonium ion), NO2+
(nitronium ion), SO2 etc.
Electron displacement effects in covalent bonds
In an organic molecule, the electron displacement may take place either under the influence of an
atom or in the presence of an attacking reagent. The important types of electron displacement effects
are inductive effect, electromeric effect, resonance effect and hyper conjugation.
1. Inductive effect (I effect):
It is a permanent effect arising due to the shifting of sigma electrons through a
carbon chain in presence of an atom or group of atom (having different electronegativity)
attached to a carbon chain. This effect propagates only through C – C σ bonds. This effect decreases
rapidly as the number of C atoms increases.
E.g. 1-chlorobutane CH3 – CH2 – CH2 – CH2 –Cl
Here Cl is more electronegative than C. So the electron pair in the C – Cl bond is shifted towards Cl
and it gets a slight –ve charge (δ-) and C gets a slight +ve charge (δ+). This carbon attracts the electron
density from the second carbon and so the 2nd carbon gets a relatively smaller positive charge (δδ+).

The inductive effect is related to the ability of substituents to either withdraw or donate electron
density to the attached carbon atom. Based on this ability, the substituents can be classified as electron-
withdrawing group (-I effect group) or electron donating groups (+I effect group) relative to hydrogen.
Groups that withdraw (attract) electrons from the carbon chain are said to have -I effect.
Example for such groups are –X (F, Cl, Br, I), nitro (-NO2), cyano (CN-), carboxy (-COOH), ester (-COOR),
aryloxy (-OAr) etc.
Groups which donate (release) electron pairs towards the carbon chain are said to have +I effect.
Example for such groups are alkyl groups like methyl (-CH3), ethyl (-CH2-CH3) etc.
2. Electromeric effect (E effect):
It is defined as the complete transfer of a shared pair of π-electrons to one of the
atoms joined by a multiple bond in presence of an attacking reagent. It is a temporary
effect. It is possible only in compounds containing multiple bonds( alkene or alkyne). This effect
cancels when the attacking reagent is removed from the reaction site. The shifting of the electrons is
shown by a curved arrow (↷).
There are two types of E effects:
a) Positive Electromeric effect (+E effect): Here the pi electrons are transferred to that atom to
which the attacking reagent gets attached.

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b) Negative Electromeric effect (-E effect): Here the pi electrons of the multiple bonds are
transferred to that atom to which the attacking reagent does not get attached.

When inductive and electromeric effects operate in opposite directions, the electromeric effect
predominates.
Differentiate between Inductive effect and Electromeric effect
Inductive Effect Electromeric Effect
It is the shifting of sigma electrons through It is the complete transfer of the shared pair of π-
a carbon chain in presence of an atom or electrons to one of the atoms joined by a multiple
group of atom attached to a carbon chain. bond in presence of an attacking reagent.
It is a permanent effect. It is a temporary effect.
It propagates only through C – C sigma It is possible only in compounds containing
bonds. multiple bonds.
Partial polarity is developed. Complete polarity is developed.
No attacking reagent is required Takes place only in presence of attacking reagent.

3. Resonance Effect (R effect) or Mesomeric effect (M effect):

It is defined as ‘the polarity (charge) produced in the molecule by the interaction of
two π-bonds or between a π-bond and lone pair of electrons present on an adjacent atom’.
The effect is transmitted through the chain.
There are two types of resonance effect (R effect):
a) Positive Resonance effect (+R effect): Here the transfer of electrons is away from an atom or
substituent group attached to the conjugated system. E.g. + R effect in phenol:

b) Negative Resonance Effect (- R effect): Here the transfer of electrons is towards the atom or
substituent group attached to the conjugated system. E.g. – R effect in nitrobenzene:

The presence of alternate single and double bonds in an open chain or cyclic system is termed as a
conjugated system.
E.g. for +R effect groups: –X (halogen), –OH, –OR, –OCOR, –NH2, –NHR, –NR2, –NHCOR etc.
E.g. for – R effect groups: – COOH, –CHO, >C=O, – CN, –NO2 etc.

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4. Hyper conjugation:
It is a permanent effect. In this effect the σ electrons of C—H bond of the alkyl
group enter into partial conjugation with the unsaturated system or with the unshared p
orbital. i.e. the σ electrons of C –H bonds get delocalised.
E.g. Ethyl cation (CH3-CH2+)

Hyper conjugation stabilizes the carbocation because electron density from the adjacent σ bond
helps in dispersing the positive charge. In general, the greater the number of alkyl groups attached to
a positively charged carbon atom, the greater is the hyper conjugation interaction and stabilization
of the cation.
Thus the relative stability of carbocations is in the order: (CH3)3C+ > (CH3)2CH+ > CH3-CH2+ > CH3+.
Here tertiary carbocation has 9, isopropyl has 6, ethyl carbocation has 3 and methyl carbocation
has zero hyper conjugative structures.
Hyper conjugation is also called no-bond resonance and it is also possible in alkenes and alkyl arenes.
Types of Organic reactions
Organic reactions can be classified into the following categories:
i. Substitution reactions
ii. Addition reactions
iii. Elimination reactions
iv. Rearrangement reactions
PURIFICATION OF ORGANIC COMPOUNDS
An organic compound may contain impurities and is essential to purify it. Various methods used
for the purification of organic compounds are based on the nature of the compound and the impurity
present in it.
The common techniques used for purification are as follows:
i. Sublimation
ii. Crystallisation
iii. Distillation
iv. Differential extraction and
v. Chromatography
1. Sublimation
It is the process of conversion of a solid substance directly to vapour by heating. It is used to
separate sublimable compounds from non-sublimable impurities.
In this method, the substance is placed in a sublimation apparatus and heated under vacuum.
Under this reduced pressure, the solid sublimes and condenses as a purified compound on a cooled
surface. The impurities left behind on the apparatus.
This method is used for the purification of naphthalene, iodine, camphor etc.
2. Crystallisation
This is one of the most commonly used techniques for the purification of solid organic compounds.
It is based on the difference in the solubilities of the compound and the impurities in a suitable
solvent. The impure compound is dissolved in a solvent in which it is sparingly soluble at room
temperature but appreciably soluble at higher temperature. The solution is concentrated to get a
nearly saturated solution. On cooling the solution, pure compound crystallises out and is removed by

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filtration. If the compound is highly soluble in one solvent and very little soluble in another solvent,
crystallisation can be satisfactorily carried out in a mixture of these solvents.
3. Distillation
This method is used to separate (i) volatile liquids from non-volatile impurities and (ii) the
liquids having sufficient difference in their boiling points. The principle of this method is that
liquids having different boiling points vapourise at different temperatures. The vapours are cooled
and the liquids so formed are collected separately.
In this method, the liquid mixture is taken in a round bottom flask and heated carefully. On boiling,
the vapours of lower boiling liquid are formed first. The vapours are condensed by using a condenser
and the liquid is collected in a receiver. The vapours of higher boiling liquid form later and it can be
collected separately. Chloroform (b.p 334 K) and aniline (b.p. 457 K) are separated by this technique.
There are different types of distillation methods. They are:
a) Fractional distillation:
Fractional distillation is used to separate two or more liquids that are miscible. It is a special type
of distillation designed to separate a mixture of two or more liquids that have different boiling
points. The process involves heating the mixture and partial condensation of the vapours along a
fractionating column. The column is set up such that components with lower boiling points pass
through the column and are collected earlier than components with higher boiling points. Repeated
vaporization and condensation result in the separation of the components of the mixture. The
efficiency of fractional distillation depends on the use of the fractionating column. The fractionating
column is packed with glass beads. It provides a large surface area for vaporization and condensation
of the liquid mixture.
Ethanol and water mixture, crude oil, toluene and cyclohexane etc. are separated by this method.
b) Distillation under reduced pressure:
This method is used to purify liquids having very high boiling points and those, which
decompose at or below their boiling points. Such liquids are made to boil at a temperature lower
than their normal boiling points by reducing the pressure on their surface. The pressure is
reduced with the help of a water pump or vacuum pump. Glycerol can be separated from spent-lye
in soap industry by using this technique.
c) Steam Distillation:
This technique is applied to separate substances which are steam volatile and are immiscible
with water. In steam distillation, steam from a steam generator is passed through a heated flask
containing the liquid to be distilled. The mixture of steam and the volatile organic compound is
condensed and collected. The compound is later separated from water using a separating funnel.
Aniline – water mixture is separated by this method.
4. Differential Extraction
When an organic compound is present in an aqueous medium, it is separated by shaking it with
an organic solvent in which it is more soluble than in water. The organic solvent and the aqueous
solution should be immiscible with each other. So they form two distinct layers which can be
separated by separating funnel. The organic solvent is later removed by distillation or by evaporation
to get back the compound.
5. Chromatography
This method is used to separate mixtures into their components, to purify compounds and
to test the purity of compounds. Here the mixture to be separated is passed through a stationary
phase, which may be a solid or a liquid. A pure solvent (sometimes a mixture of solvents or a gas) is
allowed to move slowly over the stationary phase. The moving phase is called the mobile phase. The

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components of the mixture get gradually separated from one another.

Based on the principle involved, there are mainly two types of chromatography:
(a) Adsorption chromatography, and
(b) Partition chromatography
a) Adsorption Chromatography: Adsorption chromatography is based on the fact that different
compounds are adsorbed on an adsorbent in different degrees. Commonly used adsorbents are
silica gel and alumina. Here a mobile phase is allowed to move over a stationary phase (adsorbent).
Based on the adsorbing power, the components of the mixture are adsorbed at different places over
the stationary phase. Following are two main types of chromatographic techniques based on the
principle of differential adsorption.
i) Column chromatography, and
ii) Thin layer chromatography.
i) Column Chromatography:
It involves the separation of a mixture over a column of adsorbent (stationary phase) packed in a
glass tube. The column is fitted with a stopcock at its lower end. The mixture to be separated is
passed through the column. Based on the adsorbing power, the components are adsorbed at
different places over the column. The most readily adsorbed substances are retained near the top
and others come down to various distances in the column. Then an appropriate eluant (mobile
phase) is allowed to flow down the column slowly. [Eluant is a solvent or a mixture of solvents used
to move the compounds through the column]. Thus the different components can be collected
separately.
ii) Thin Layer Chromatography (TLC):
It is another type of adsorption chromatography. It involves the separation of substances of a
mixture over a thin layer of an adsorbent coated on a glass plate. A thin layer of an adsorbent like
silica gel or alumina is coated over a glass plate of suitable size. The plate is known as thin layer
chromatography plate or chromaplate.
The solution of the mixture to be separated is applied as a small spot, 2 cm above one end of the
TLC plate. The glass plate is then placed in a closed jar containing the eluant. As the eluant rises up
the plate, the components of the mixture move up along with the eluant to different distances
depending on their degree of adsorption and separation takes place. The relative adsorption of each
component of the mixture is expressed in terms of its retardation factor (Rf value).
Rf = Distance moved by the substance from base line (x)
Distance moved by the solvent from base line (y)
The spots of coloured compounds are visible on TLC plate due to their original colour. The spots of
colourless compounds can be detected by putting the plate under ultraviolet light.
b) Partition Chromatography:
It is based on continuous differential partitioning of components of a mixture between stationary
and mobile phases. Paper chromatography is a type of partition chromatography.
In paper chromatography, a special quality paper known as chromatography paper is used.
Chromatography paper contains water trapped in it, which acts as the stationary phase. A strip of
chromatography paper, spotted at the base with the solution of the mixture, is suspended in a
suitable solvent or a mixture of solvents. This solvent acts as the mobile phase. The solvent rises up
the paper by capillary action and flows over the spot. The paper selectively retains different
components according to their differing partition in the two phases. The paper strip is known as a
chromatogram. The spots of the separated coloured compounds are visible at different heights from
the position of initial spot on the chromatogram. These spots can be visible by u.v. light or by
spraying suitable reagents.

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QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS

An organic compound mainly contains carbon and hydrogen. Some compounds may also contain
oxygen, nitrogen, sulphur, halogens and phosphorus.
Detection of Carbon and Hydrogen
Organic compound is heated with copper (II) oxide [CuO]. Carbon present in the compound is oxidised
to carbon dioxide and hydrogen to water. CO2 can be tested by passing through lime-water, which turns
milky and water can be tested with anhydrous copper sulphate, which turns blue.
C + 2CuO Δ → 2Cu + CO2
2H + CuO Δ → Cu + H2O
CO2 + Ca(OH)2 → CaCO3↓ + H2O
Detection of Nitrogen, Sulphur and Halogens – Lassaigne’s Test
Nitrogen, sulphur and halogens present in an organic compound are detected by “Lassaigne’s
test”. Here the organic compound is fused with metallic sodium in a fusion tube. It is then plunged
into distilled water taken in a china dish. The solution is boiled and filtered. The filtrate is known
as sodium fusion extract.
Principle: In an organic compound, nitrogen, sulphur and halogen atoms are present in covalent form.
By heating with metallic sodium, these elements are converted to ionic form as follows:
Na + C + N Δ → NaCN
2Na + S Δ → Na2S
Na + X Δ → Na X (X = Cl, Br or I)
For the detection of the elements, the following tests are done:
No. Experiment Observation Inference

1. To one part of sodium fusion extract add Blue or green Presence of

freshly prepared ferrous sulphate colouration or nitrogen
(FeSO4) solution. Heated to boiling, precipitate (ppt)
cooled and acidified with dil. H2SO4.

2. A little of the sodium fusion extract is White ppt soluble in Presence of

acidified with dil. HNO3 and then silver ammonium hydroxide Chlorine
nitrate (AgNO3) is added. (NH4OH)

Pale yellow ppt slightly Presence of

soluble in NH4OH Bromine

Yellow ppt insoluble in Presence of

NH4OH Iodine

3. To a little of the sodium fusion extract, Violet colouration Presence of

add sodium nitroprusside solution sulphur

Test for Phosphorus

The organic compound is heated with an oxidising agent like sodium peroxide. The phosphorus
present in the compound is oxidised to phosphate. The solution is boiled with nitric acid and then
treated with ammonium molybdate. A yellow colouration or precipitate indicates the presence of
phosphorus.
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QUANTITATIVE ANALYSIS OF ORGANIC COMPOUNDS

The percentage composition of elements present in an organic compound is determined by the
following methods:
1. Estimation of Carbon and Hydrogen
Carbon and hydrogen are estimated by Liebig’s combustion method. In this method, a known mass of
an organic compound is burnt in the presence of excess of oxygen and copper(II) oxide. Then carbon is
oxidised to CO2 and hydrogen is oxidised to H2O.
CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O
The water so produced is absorbed in a weighed U-tube containing anhydrous calcium chloride and
carbon dioxide is absorbed in another U-tube containing concentrated solution of potassium hydroxide.
These tubes are connected in series. The increase in masses of calcium chloride and potassium
hydroxide gives the amounts of water and carbon dioxide from which the percentages of carbon and
hydrogen are calculated.
Calculations:
Let the mass of organic compound be w g, mass of water and carbon dioxide produced be m1 and m2 g
respectively.
2 x 𝑚 x 100
Percentage of hydrogen = 181x w %
12 x 𝑚2 x 100
Percentage of carbon = %
44 x w

2. Estimation of Nitrogen
There are two methods for estimation of nitrogen: (i) Dumas method and (ii) Kjeldahl’s method.
i) Dumas method:
Here the organic compound is heated with copper oxide in an atmosphere of carbon dioxide so that
free nitrogen, carbon dioxide and water are produced.
CxHyNz + (2x + y/2) CuO → x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
This mixture of gases is collected over an aqueous solution of potassium hydroxide which absorbs
carbon dioxide. Nitrogen is collected in the upper part of the graduated tube.

Calculations:
Let the mass of organic compound = w g
Volume of nitrogen collected = V1 mL
Room temperature = T1 K
Volume of nitrogen at STP = P1V1 x 273 = V mL
760 × T1
Where P1 and V1 are the pressure and volume of nitrogen gas.
P1= Atmospheric pressure – Aqueous tension

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We know that 22400 mL N2 at STP weighs 28 g.

Therefore, V mL N2 at STP weighs = 28 x V g
22400
Percentage of nitrogen = 28 x V x 100 %
22400 x w
ii) Kjeldahl’s method:
Here the organic compound containing nitrogen is heated with concentrated sulphuric
acid. Nitrogen in the compound gets converted to ammonium sulphate. The resulting acidic
mixture is then heated with excess of sodium hydroxide. The liberated ammonia gas is
absorbed in an excess of standard solution of sulphuric acid. The amount of ammonia
produced is determined by estimating the amount of sulphuric acid consumed in the
reaction. It is done by estimating unreacted sulphuric acid left after the absorption of
ammonia by titrating it with standard alkali solution. The difference between the initial
amount of acid taken and that left after the reaction gives the amount of acid reacted
with ammonia.
NaOH
Organic compound + H2SO4 → (NH4)2SO4 → Na2SO4 + NH3 + H2O
2NH3 + H2SO4 → (NH4)2SO4
Calculations:
Let the mass of organic compound taken = w g
Volume of H2SO4 of molarity M, taken = V mL
Volume of NaOH of molarity M, used for titration of excess of H2SO4 = V1 mL
V1mL of NaOH of molarity M = V1/2 mL of H2SO4 of molarity M
Volume of H2SO4 of molarity M unused = (V - V1/2) mL = y mL
y mL of H2SO4 of molarity M = 2y mL of NH3 solution of molarity M.
1000 mL of 1 M NH3 solution contains 17g NH3 or 14 g of N
14 x M x 2y
2y mL of NH3 solution of molarity M contains gN
1000
14 x M x 2y x 100
Percentage of N = %
1000 x w
Note: Kjeldahl’s method is not applicable to compounds containing nitrogen in nitro and azo groups and
nitrogen present in the ring (e.g. pyridine) as nitrogen of these compounds does not change to
ammonium sulphate under these conditions.

3. Estimation of halogens (Carius method):

Here a known mass of an organic compound is heated with fuming nitric acid in the presence of silver
nitrate contained in a hard glass tube known as Carius tube, in a furnace. Carbon and hydrogen present
in the compound are oxidised to carbon dioxide and water. The halogen present forms the
corresponding silver halide (AgX). It is filtered, washed, dried and weighed.
Calculations:
Let the mass of organic compound taken = w g
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of halogen
Atomic mass of halogen x m1
Mass of halogen in m1g of AgX = g
Molar mass of AgX
Atomic mass of halogen x m1 𝑥 100
Percentage of halogen = %
Molar mass of AgX x w

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4. Estimation of Sulphur (Carius method):

A known mass of an organic compound is heated in a Carius tube with sodium peroxide or
fuming nitric acid. Sulphur present in the compound is oxidised to sulphuric acid. It is precipitated as
barium sulphate by adding excess of barium chloride solution. The precipitate is filtered, washed, dried
and weighed. The percentage of sulphur can be calculated from the mass of barium sulphate (BaSO4).
Calculations:
Let the mass of organic compound taken = w g and the mass of barium sulphate formed = m1 g
1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur
32 x m1
m1 g BaSO4 contains g sulphur
233
32 x m1 𝑥 100
Percentage of sulphur = %
233 x w
5. Estimation of Phosphorus
A known mass of an organic compound is heated with fuming nitric acid. Phosphorus present in the
compound is oxidised to phosphoric acid. It is precipitated as ammonium phosphomolybdate
[(NH4)3PO4.12MoO3] by adding ammonia and ammonium molybdate.
Calculations:
Let the mass of organic compound taken = w g and mass of ammonium phosphomolydate = m1g
Molar mass of (NH4)3PO4.12MoO3 = 1877 g
31 x m1 𝑥 100
Percentage of phosphorus = %
1877 x w

6. Estimation of Oxygen
The percentage of oxygen in an organic compound is usually found by difference between the total
percentage composition (100) and the sum of the percentages of all other elements.
i.e. percentage of oxygen = 100 – sum of the percentage of all the other elements.

Q1) On complete combustion, 0.246g of an organic compound gave 0.198g of CO2

and 0.1014g of H2O. Determine the percentage composition of carbon and
hydrogen in the compound.
Ans: Mass of organic compound (m) = 0.246 g
Mass of CO2 formed (m1) = 0.198 g
12 x 𝑚2 x 100 12 x 0.198 x 100
Percentage of carbon = % = % = 21.95%
44 x w 44 x 0.246
Mass of water formed (m2) = 0.1014 g
2 x 𝑚1 x 100 2 x 0.1014 x 100
Percentage of hydrogen = % = % = 4.58 %
18 x w 18 x 0.246
Q2) In the Carius method of estimation of halogen, 0.15g of an organic
compound gave 0.12g of AgBr. Find the percentage of Br in the compound.
Ans: Mass of organic compound (m) = 0.15 g
Mass of AgBr formed (m1) = 0.12 g
Atomic mass of Br = 80
Molar mass of AgBr = 108+ 80 = 188 g/mol
Atomic mass of Br x m1 𝑥 100 80 x 0.12 x 100
Percentage of Br = %= % = 34.04 %
Molar mass of AgBr x w 188 x 0.15
***************************************************************************************************

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9. HYDROCARBONS
Organic compounds containing carbon and hydrogen atoms only are called hydrocarbons.
Depending on the types of C-C bond, they can be classified into three – saturated, unsaturated and
aromatic hydrocarbons. Saturated hydrocarbons are also called alkanes. They contain only C-C single
bonds. Unsaturated hydrocarbons contain atleast one carbon-carbon double bond (alkene) or carbon-
carbon triple bond (alkyne). Aromatic hydrocarbons are a special type of cyclic compounds. They are
also called arenes.
ALKANES
Alkanes are saturated open chain hydrocarbons containing carbon-carbon single bonds. They
form a homologous series. Their general molecular formula is CnH2n+2. In alkanes, all the C atoms are sp3
hybridised. So each C atom has a regular tetrahedral shape.
Alkanes do not react with acids, bases and other reagents under normal conditions. So they are
also called paraffins. (In Latin paraffin means little affinity).
Isomerism in Alkanes
Alkanes show two types of structural isomerism – chain isomerism and position isomerism.
Chain isomers differ in the carbon skeleton. i.e arrangement of carbon atoms in the chain.
E.g.: The chain isomers of alkane with molecular formula C5H12 are:
CH3-CH2-CH2-CH2-CH3 (n-pentane)
CH3-CH-CH2-CH3 (isopentane)
CH3
CH3
CH3-C-CH3 (neopentane)
CH3
Position isomers differ in the position of the side chain or branch.
E.g. The position isomers of alkane with molecular formula C6H14 are:
CH3-CH2-CH2-CH2-CH-CH3 (2-Methylpentane)
CH3
CH3-CH2-CH-CH2-CH3 (3-Methylpentane)
CH3
Preparation of alkanes
1. From unsaturated hydrocarbons: Alkenes and alkynes add Hydrogen in presence of finely
divided catalysts like Ni, Pd or Pt to form alkanes. This process is called hydrogenation.

2. From alkyl halides:

a) Alkyl halides on reduction with zinc and dil. HCl, we get alkanes.
𝑍𝑛/𝐻𝐶𝑙
R-X + H2 → R-H + HX

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b) Wurtz reaction:
Alkyl halides react with metallic sodium in dry ether to form alkanes. This
reaction is known as Wurtz reaction. The alkane so formed contains double the number of
C atoms than that present in the alkyl halide. Hence this method is used for the preparation of
alkanes with even number of carbon atoms.
𝐷𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
R-X + 2 Na + X -R → R-R + 2 NaX

When two different alkyl halides are used, we get a mixture of alkanes.
3. From carboxylic acids:
a) Decarboxylation: Sodium salt of carboxylic acids (R-COONa) on heating with soda
lime (a mixture of NaOH and CaO), we get an alkane containing one carbon atom less
than that of the carboxylic acid. This process is known as decarboxylation, since it
involves the elimination of a CO2 molecule from the carboxylic acid (R-COOH).
CaO
R-COONa + NaOH → R-H + Na2CO3
Cao
E.g. CH3COONa + NaOH → CH4 + Na2CO3
Sodium acetate methane
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.
2CH3COONa + 2H2O → CH3 – CH3 + 2CO2 + 2NaOH + H2
(Sod. Acetate) (Ethane)
Physical Properties
Boiling point of alkanes increase with increase of molecular mass (or with number of C atoms).
This is because in alkanes there is only weak van der Waal’s force of attraction between different
molecules. As the molecular size increases, the surface area increases and hence van der Waal’s force
increases. So the boiling point increases.
The boiling point of isomeric alkanes decreases with branching. As the branching increases, the
molecule attains the shape of a sphere. So the surface area decreases and hence the b.p. So among
three isomeric pentane boiling point decreases in the order: n-pentane > isopentane > neopentane.
CH3
CH3-CH2-CH2-CH2-CH3 > CH3-CH-CH2-CH3 > CH3-C-CH3
CH3 CH3
(n-pentane) (isopentane) (neopentane)
Chemical Properties
1. Substitution reactions
These are reactions in which hydrogen atom of an alkane is replaced by other atoms or atom groups.
E.g. when an alkane is treated with halogen in the presence of diffused sunlight or uv light,
we get haloalkane. This reaction is known as halogenation reaction.
ℎ𝜐
CH4 + Cl2 → CH3Cl + HCl
(monochloromethane or methyl chloride)

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ℎ𝜐
CH3Cl + Cl2 → CH2Cl2 + HCl
(dichloromethane or methylene chloride)
ℎ𝜐
CH2Cl2 + Cl2 → CHCl3 + HCl
(trichloromethane or chloroform)
ℎ𝜐
CHCl3 + Cl2 → CCl4 + HCl
(tetrachloromethane or carbon tetrachloride)
Mechanism
Halogenations takes place by free radical chain mechanism and it involves three steps – initiation,
propagation and termination.
i) Initiation step: The reaction is initiated by the homolysis of chlorine molecule in presence of
sunlight.

ii) Propagation step: The chlorine free radical attacks the methane molecule and form methyl free
radical and HCl.

The methyl radical then attacks the second Cl2 molecule to form CH3Cl and Chlorine free radical.

The above two steps repeat and thus the reaction propagates.

iii) Termination step: The reaction stops after some time due to any one of the following reactions:

2. Combustion (Oxidation):
On combustion in presence of air or oxygen, alkanes give CO2, H2O and large amount of heat.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) + heat
The general combustion equation for any alkane is:
CnH2n+2 + (3n+1)/ 2 O2 → nCO2 + (n+1) H2O
Incomplete combustion of alkanes with insufficient amount of air or O2 gives carbon black.
3. Controlled Oxidation:
Alkanes on heating with O2 at high pressure and in presence of suitable catalysts to form
different products like alcohol, aldehyde or carboxylic acid.
𝐶𝑢/523𝐾/100 𝑎𝑡𝑚
2 CH4 + O2 → 2 CH3OH
(Methanol)
Mo2 O3 /∆
CH4 + O2 → HCHO + H2O
(formaldehyde)
(CH3 𝐶𝑂𝑂)3 Mn/∆
2 CH3-CH3 + 3 O2 → 2 CH3COOH + 2 H2O
(Acetic acid or ethanoic acid)

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4. Isomerisation: n-Alkanes on heating in the presence of anhydrous aluminium chloride

and hydrogen chloride gas isomerise to branched chain alkanes.
𝐴𝑛ℎ𝑦𝑑𝑟𝑜𝑢𝑠 𝐴𝑙𝐶𝑙3 /𝐻𝐶𝑙
CH3-(CH2)4-CH3 → CH3-CH-CH2-CH2-CH3 + CH3-CH2-CH-CH2-CH3
CH3 CH3
(n-hexane) (2-Methylpentane) (3-Methyl pentane)
5. Aromatization: n-Alkanes having six or more carbon atoms on heating to 773K at 10 to
20 atmospheric pressure in the presence of oxides of vanadium, molybdenum or
chromium supported over alumina, we get aromatic compounds. This reaction is
known as aromatization or reforming.

CH3-(CH2)4-CH3 Cr2O3 or V2O5 or Mo2O3

n-hexane 773K, 10-20 atm
Benzene
6. Pyrolysis: Alkanes having six or more carbon atoms on heating at higher temperature
decompose to form lower alkanes, alkenes etc. This reaction is known as pyrolysis .
C6H12 + H2

C6H14 773K C4H8 + C2H6

C3H6 + C2H4 + CH4

Conformations of Alkanes
Alkanes contain carbon-carbon sigma (σ) bonds. Since, electron distribution of the sigma bonds is
symmetrical around the bond axis, rotation around C–C bond is allowed. This rotation changes the
spatial arrangements of atoms attached to C atoms. These different spatial arrangements of
atoms arising due to free rotation around a C-C single bond are called conformations or
conformers or rotamers.
Conformations of Ethane
Ethane contains a C-C σ bond and each carbon atom contains three hydrogen atoms. Due to free
rotation of C atoms around the single bond, the spatial arrangement of hydrogen atoms attached to the
C atoms change. Thus ethane can show an infinite number of conformational isomers.
If we fix one carbon atom and rotate the other, there arise two extreme cases called
eclipsed and staggered conformations.
In eclipsed conformation, the hydrogen atoms attached to each carbon atoms are
closed together as possible. Or, here the hydrogen atoms of the 2nd carbon atoms are
exactly behind that of the first.
In staggered conformation, the hydrogen atoms are far apart as possible. Any
conformations between eclipsed and staggered conformations are called skew conformations.
Staggered conformation is stabler than eclipsed form. This is because in staggered
form, the electron clouds of carbon-hydrogen bonds are very far apart. So there is
minimum repulsive forces, minimum energy and maximum stability. But in eclipsed form, the
electron clouds are close to each other. So the repulsion is maximum and the stability is minimum.
Eclipsed and staggered conformations can be represented by Sawhorse and Newman projection
formulae.

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1. Sawhorse projections:
Here the molecule is viewed along the molecular axis. C–C bond is denoted by a longer straight line.
The front carbon is shown at the lower end of the line and the back carbon is shown at the upper end.
Each carbon has three lines at an angle of 120° corresponding to three hydrogen atoms .
Sawhorse projections of eclipsed and staggered conformations of ethane are as follows:

2. Newman projections:
Here the molecule is viewed at the C–C bond head on (i.e. from the front side). The front carbon
atom is represented by a point. Three hydrogen atoms attached to this carbon atom are shown by three
lines drawn at an angle of 120° to each other. The back carbon atom is represented by a circle and the
three hydrogen atoms are shown attached to it are denoted by shorter lines drawn at an angle of 120°
to each other.
The Newman’s projections for eclipsed and staggered conformations of ethane are as follows:

ALKENES
Alkenes are unsaturated hydrocarbons containing at least one C=C (carbon-carbon double bond).
They are also known as olefins (oil forming) since the first member, ethylene or ethene (C2H4) forms an
oily liquid on reaction with chlorine. The general formula for alkenes is CnH2n.
Isomerism in alkenes
Alkenes show structural and stereo isomerism. The important structural isomerism shown by
alkenes are chain isomerism and position isomerism.
E.g. for chain isomers with molecular formula C4H8 are:
CH3-CH2-CH=CH2 (Butene or Butylene)
CH3-C=CH2 (2-methylprop-1-ene or Isobutylene)
CH3
E.g. for position isomers with molecular formula C4H8 are:
CH3-CH2-CH=CH2 and CH3-CH=CH-CH3
(but-1-ene) (but-2-ene)
The stereoisomers have same atom to atom bond but they differ only in the spatial arrangement of
atoms or groups. The stereoisomerism shown by alkenes is geometrical isomerism.

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Geometrical Isomerism
The isomerism arising due to the difference in the spatial arrangement of atoms
around carbon-carbon double bond is called geometrical isomerism. Such isomers are called
geometrical isomers. It is a type of stereo isomerism.
Geometrical isomerism arising due to the restricted rotation about carbon-carbon
double bond. There are two types of geometrical isomers – cis isomer and trans isomer.
Isomer in which identical atoms or groups are on the same side of the double bond is
called cis isomer. If the identical groups or atoms are on the opposite side of the double
bond, it is called trans isomer.
Compounds with general formula YX C = C XY can show geometrical isomerism as follows:

cis isomer trans isomer

E.g. But-2-ene

Due to different arrangement of atoms or groups in space, these isomers differ in their physical
properties like melting point, boiling point, dipole moment, solubility etc.
Cis form of alkene is found to be more polar than the trans form. In trans form, the bond dipoles
are in opposite directions and so they get cancelled each other.

In the case of solids, the trans isomer has higher melting point than the cis form.
PREPARATION OF ALKENES
1. From Alkynes: Alkynes on partial reduction with dihydrogen in the presence of palladised
charcoal partially deactivated with sulphur compounds or quinoline give alkenes. Partially
deactivated palladised charcoal is known as Lindlar’s catalyst. Alkenes thus obtained are having
cis geometry.

If we use sodium in liquid ammonia as the reducing agent, we get trans alkene.

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2. From Alkyl halides:

Alkyl halides (R-X) on heating with alcoholic potash, eliminate one molecule of
hydrogen halide to form alkenes. This reaction is known as dehydrohalogenation (i.e.,
removal of hydrogen halide from a compound). Since hydrogen atom is eliminated from the β
carbon atom, the reaction is also known as β-elimination reaction.
Alc.KOH
CH3-CH2X → CH2 = CH2 + HX
Alc.KOH
CH3-CH2-CH2Br→ CH3-CH = CH2 + HBr
3. From vicinal dihalides:
Dihalides in which halogen atoms are attached to two adjacent carbon atoms are known as
vicinal (vic) dihalides. Vicinal dihalides on treatment with zinc metal lose a molecule of ZnX2
to form an alkene. This reaction is known as dehalogenation (i.e. elimination of halogen
molecule from a compound).
CH2Br-CH2Br + Zn → CH2 = CH2 + ZnBr2
(vic-ethylene (ethene)
dibromide)
CH3-CHBr-CH2Br + Zn → CH3-CH = CH2 + ZnBr2
(1,2-Dibromopropane) (Propene)
4. From alcohols:
Alcohols when heated with concentrated sulphuric acid undergo dehydration
(elimination of water molecule) to form alkenes. This reaction is also the example of β-elimination
reaction since –OH group is eliminated from the β-carbon atom.
Conc.H2 SO4
CH3-CH2-OH → CH2 = CH2 + H2O
Chemical Properties
1. Addition of hydrogen: Alkenes add hydrogen in presence of finely divided Ni, Pd or Pt to form
alkanes.
Ni
CH2 = CH2 + H2 → CH3-CH3
2. Addition of halogen: Alkenes add halogen (Cl2 orBr2) to form vicinal dihalides.
CH2 = CH2 + X2 → CH2X-CH2X
When Br2 dissolved in CCl4 (carbon tetrachloride) is added to unsaturated
compounds (alkenes or alkynes), the reddish orange colour of bromine solution is
discharged. This reaction is used as a test for unsaturation.
CH2 = CH2 + Br2 → CH2Br-CH2Br
3. Addition of hydrogen halide:
Alkenes add hydrogen halide to form alkyl halides.
CH2 = CH2 + HX → CH3-CH2X
CH2 = CH2 + HBr → CH3-CH2Br
(ethene) (Bromoethane)
CH3-CH = CH-CH3 + HBr → CH3-CH2-CHBr-CH3
(But-2-ene) (2-Bromobutane)

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Addition of HBr to unsymmetrical alkenes (Markovnokov’s Rule)

When HBr is added to propene, we get 2 products – 1-bromopropane and 2-bromopropane.

Here the major product is determined by a rule called Markovnikov rule. The rule states that
“when an unsymmetrical reagent is added to an unsymmetrical alkene, the negative part of
the addendum (adding molecule) gets attached to the double bonded carbon with lesser
number of hydrogen atoms”. Thus in the above reaction 2-bromopropane is the major product.
Mechanism:
(i) Hydrogen bromide provides an electrophile H+, which attacks the double bond to form carbocation.

(ii) Since secondary carbocation (b) is more stable than the primary carbocation (a), it is attacked by
Br– ion to form the product as follows :

Anti Markovnikov addition or peroxide effect or Kharash effect

In presence of organic peroxide (e.g. acetyl peroxide [(CH3-CO)2O2], benzoyl peroxide
[(C6H5CO)2O2] etc.), addition of HBr to unsymmetrical alkenes takes place against
Markovnikov rule. i.e. in such cases, the negative part of the reagent gets attached to the
double bonded carbon atom with greater number of hydrogen atom. This is known as
peroxide effect or Kharash effect or anti-Markovnikov addition reaction.
(C6 H3 CO)2 O2
e.g. CH3-CH= CH2 + HBr → CH3-CH2-CH2Br
Propene 1-bromopropane
Mechanism:
Peroxide effect proceeds via free radical chain mechanism as follows:
(i) Homolysis of benzoyl peroxide produces phenyl free radical.

(ii) Phenyl free radical reacts with HBr to form Bromine free radical.

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(iii) Bromine free radical attacks propene to form a primary and secondary free radicals. Since
secondary free radical is stabler, it will be the major one.

(iv) These free radicals react with H-Br to form the products and Bromine free radical.

4. Addition of sulphuric acid: Cold concentrated sulphuric acid adds to alkenes and form alkyl
hydrogen sulphate. The reaction takes place in accordance with Markovnikov rule.

5. Addition of water:
Alkenes add water in presence of a few drops of concentrated sulphuric acid to form alcohols.
The reaction occurs according to the Markovnikov rule.
Conc.H2 SO4
CH3-CH=CH2 + H2O → CH3-CH(OH)- CH3
Propene 2-propanaol
6. Oxidation:
i) When oxidised using cold and dilute aqueous solution of potassium permanganate
(KMnO4) [commonly called Baeyer’s reagent], alkenes give vicinal glycols.

When KMnO4 is added to alkene, its pink colour gets discharged. So this reaction is
also used as a test for unsaturation.
ii) Acidified potassium permanganate (KMnO4) or acidified potassium dichromate (K2Cr2O7)
oxidises alkenes to ketone or acids depending on the nature of the alkene.
KMnO4 /H+
CH3-CH= CH2 → CH3-COOH + CO2 + H2O
(Propene) (Acetic acid)

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KMnO4 /H+
CH3-CH=CH-CH3 → 2 CH3-COOH
(But-2-ene) [Ethanoic acid (acetic acid)]
KMnO4 /H+
(CH3)2C = CH2 → CH3-CO-CH3 + CO2 + H2O
(2- Methylpropene) [Propanone (acetone)]

7. Ozonolysis: Alkenes add ozone to form an ozonide which on hydrolysis in presence of

Zn to form carbonyl compounds (Aldehydes or ketones).

Zn/H2O

Zn/H2O

8. Polymerisation: The complex organic molecules formed by the combination of simple

molecules are called polymers (macromolecules) and the reaction is called
polymerisation reaction. The simple molecule from which a polymer is formed is called
monomer.
Polymerisation reaction
n Monomers → Polymer

ALKYNES
They are unsaturated hydrocarbons containing at least one C ≡ C bond [carbon-carbon triple
bond]. Their general formula is CnH2n-2. The first member of alkyne series is ethyne commonly called
acetylene (C2H2). Other members are considered as the derivatives of acetylene and so alkynes are also
called Acetylenes. In alkynes, the triple bonded carbon atoms are sp hybridized and hence are linear.
Isomerism in Alkynes
Alkynes show two types structural isomerism – Position isomerism and chain isomerism.
Position isomers of C4H6 are:
CH3-CH2-C≡CH and CH3-C≡C-CH3
(but-1-yne) (but-2-yne)
Chain isomers of C5H8 are:
CH3-CH2-C≡C-CH3 and CH3-CH-C≡CH
CH3
(pent-2-yne) (2-methylbut-1-yne)

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Preparation of alkynes
1. From calcium carbide (CaC2): On large scale, ethyne is prepared by treating calcium
carbide with water. Calcium carbide is prepared by heating quick lime (CaO) with coke.
CaCO3 → CaO + CO2
(lime stone) (quick lime)
CaO + 3C → CaC2 + CO
CaC2 + 2H2O → C2H2 + Ca(OH)2
(calcium carbide) (acetylene)
2. From vicinal dihalides: Vicinal dihalides undergo dehydrohalogenation on treatment with
alcoholic KOH to form alkenyl halide which on treatment with sodamide (NaNH2) to form alkyne.
NaNH2
CH2Br-CH2Br + KOH (alc.) → CH2 = CHBr → CH ≡ CH
1,2-dibromoetane Ethylene bromide Ethyne (acetylene)
NaNH2
CH3-CHCl-CH2Cl + KOH (alc.) → CH3-CH=CHCl → CH3-C≡CH
(1,2-Dichloropropane) (1-chloroprop-1-ene) (propyne)
Chemical Properties
1. Acidic character: 1-alkynes are acidic in nature. This is because in alkynes, the triple
bonded carbon atoms are sp hybridized. Due to the greater s-character (50%), the sp
hybridised orbitals of carbon atoms in ethyne molecules have highest
electronegativity. So they attract the shared electron pair of the C-H bond to a
greater extent and hence the hydrogen atom is removed as H+. So 1-alkynes are acidic
in nature.
E.g. Acetylene on reaction with Na metal, we get sodium acetylide (monosodium ethynide) and
hydrogen gas.

This on further reacts with Na metal to form disodium acetylide (disodium ethynide) and H 2.

This reaction is not shown by alkenes and alkanes. Hence it is used for distinction between alkynes
and alkenes or alkanes. Also this reaction is used to distinguish 1-alkynes from other isomeric
alkynes. E.g. 1-butyne and 2-butyne can be distinguished by using this reaction.
2. Addition reactions:
i. Addition of H2:
Ni/Pt/Pd H2 /Ni
HC≡CH + H2 → [H2C = CH2] → CH3-CH3
Ethyne (acetylene) Ethene Ethane
𝑁𝑖 H2 /Ni
CH3-C≡CH + H2 → CH3-CH=CH2 → CH3-CH2-CH3
Propyne Propene Propane
ii. Addition of halogen:
CCl4 𝐵𝑟2 /CCl4
CH≡CH + Br2 → CHBr=CHBr → CHBr2-CHBr2
Ethyne 1,2-dibromoethane 1,1,2,2-tetrabromoethane
Reddish orange colour of the solution of bromine in carbon tetrachloride is decolourised. This is used as
a test for unsaturation.

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iii. Addition of hydrogen halide:

HBr
CH≡CH + HBr → CH2=CHBr → CH3-CHBr2
(gem-dihalide)

iv. Addition of water:

On warming with water, alkynes add one molecule of water in presence of dil.
H2SO4 and mercuric sulphate at 333K to form carbonyl compounds (aldehydes or
ketones). Acetylene gives acetaldehyde, while all other alkynes give ketones during
this reaction.
Dil.H2 SO4 /Hg𝑆𝑂4 /333 K Isomerisation
CH≡CH + H2O → CH2=CH-OH → CH3-CHO
Acetylene Ethanal (Acetaldehyde)
𝐻𝐺 2+ /𝐻 + /333 𝐾
CH3-C≡CH + H2O → CH3-CO-CH3
(Propyne) (Propanone or acetone)
3. Polymerisation
a) Linear polymerisation: Ethyne undergoes linear polymerisation under suitable conditions to form
polyethyne or polyacetylene.
Polymerisation
n CH≡CH →
acetylene (Ethyne) Polyacetylene (Polyethyne)
Under special conditions, this polymer conducts electricity. Thin film of polyacetylene can be used as
electrodes in batteries. These films are good conductors, lighter and cheaper than the metal conductors.

b) Cyclic polymerisation: Ethyne (acetylene) on passing through red hot iron tube at 873K,
undergoes cyclic polymerisation to form benzene (C6H6).
Red hot Iron tube/873 K
3 C2H2 → C6H6 OR,

AROMATIC HYDROCARBONS (ARENES)

Most of the aromatic compounds have pleasant smell (In Greek aroma means pleasant smelling)
and most of them contain benzene ring. Aromatic compounds containing benzene ring are called
benzenoid compounds and those which do not contain benzene ring are called non-benzenoid
compounds.
Structure of Benzene
Benzene was first isolated by Michael Faraday and its structure was first deduced by August Kekulé.
The molecular formula of benzene is C6H6, which indicates a high degree of unsaturation. But
benzene was found to be a stable molecule and form a triozonide which indicates the presence of three

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double bonds. Also it produces only one monosubstituted derivative which indicates that all the six
carbon and six hydrogen atoms of benzene are identical.
On the basis of these observations, August Kekulé proposed the following structure for benzene
having cyclic arrangement of six carbon atoms with alternate single and double bonds.

The Kekule structure indicates the possibility of two isomeric 1,2-disubstituted derivatives.
X X
X X

But actually these two structures are identical or, benzene forms only one 1,2,-disubstituted derivative.

In order to overcome this problem, Kekule suggested the concept of oscillating nature of double
bonds in benzene.

Kekule structure could not explain the stability of benzene and the preference of benzene to
substitution reaction rather than addition reaction.
Resonance concept of Benzene
According to this concept, benzene is a hybrid of the following two resonance structures.

The actual structure of benzene is not A or B. It is in between these two resonating structures. So
benzene is denoted by a hexagon with a dotted circle, which represents the delocalised π-electrons.
Orbital Overlap Concept of Benzene
In Benzene all the six carbon atoms are sp2 hybridized. Two sp2 hybrid orbitals of each carbon
atom overlap with sp2 hybrid orbitals of adjacent carbon atoms to form six C—C sigma bonds which are
in the hexagonal plane. The remaining one sp2 hybrid orbital of each carbon atom overlaps with 1s
orbital of hydrogen atom to form six C—H sigma bonds.
Now each carbon atom contains one unhybridised p orbital perpendicular to the plane of the
ring. They overlap laterally to form three π-bonds. There are two possible overlapping.

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These give two Kekule structures with localized π electrons. But in benzene all the C-C bonds are
identical and the bond length is 139 pm. To explain this, it is suggested that the p-orbitals of all the C
atoms overlap each other. Thus in benzene, there is an electron cloud in the form two rings one above
and one below the hexagonal ring as follows:

So the six π electrons are delocalised and can move freely about the six carbon nuclei. Presence of
delocalised π electrons in benzene makes it more stable. The delocalised
π electrons can be denoted by a circle inside a hexagonal ring.
So benzene is best represented as:

Aromaticity – Huckel Rule

Aromaticity is defined by a rule called ‘Huckel rule’. According to this rule, “cyclic,
planar, conjugated systems containing (4n+2) π electrons are aromatic”. Where n is the
number of rings. n may be 1,2,3,….
For benzene n = 1, so it should contain 6 delocalised π electrons. If n = 2, the number of
delocalised π electrons =10 and so on. Example for some aromatic compounds are:

Isomerism in Disubstituted benzene

There are three position isomers for disubstituted benzene. It can be 1,2 or 1,3 or 1.4 isomers.
1,2 disubstituted isomer is called ortho isomer, 1,3 isomer is called meta isomer and 1,4 isomer is called
para isomer.
E.g. xylene (Dimethyl benzene)

Preparation of Benzene
1. Cyclic polymerisation of ethyne (acetylene): When acetylene gas is passed mthrough red
hot iron tube at 873 K, we get benzene.
Red hot Iron tube/873 K
3 C2H2 → C6H6

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2. Decarboxylation of aromatic acids: Sodium salt of benzoic acid on heating with sodalime
gives benzene.

3. Reduction of phenol: Phenol vapours are passed over heated zinc dust, it is reduced to
benzene.

Chemical Properties
Aromatic compounds generally undergo electrophilic substitution reactions. Under special conditions,
they can also undergo addition and oxidation reactions.
I) Electrophilic Substitution Reactions
These are reactions in which a weak electrophile is replaced by a strong electrophile. The
important electrophilic substitution reactions are Nitration, Sulphonation, Halogenation and
Friedel-Crafts alkylation and acylation.
1. Nitration: It is the introduction of nitro (-NO2) group to a benzene ring. For this
benzene is heated with a mixture of conc. HNO3 and conc. H2SO4 (nitrating
mixture).

2. Halogenation: It is the introduction of halo (-X) group to a benzene ring. For this
benzene is treated with a halogen (Cl2 or Br2) in presence of Lewis acids like
anhydrous FeCl3, FeBr3 or AlCl3.

3. Sulphonation: It is the introduction of sulphonic acid (-SO3H) group to a

benzene ring. It is carried out by heating benzene with fuming sulphuric
acid (H2S2O7 or oleum).

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4. Friedel-Craft’s reaction: It is the introduction of alkyl (-R) group or acyl (-CO-R) group
to a benzene ring. It is of two types:
a) Friedel-Craft’s Alkylation reaction: It is the introduction of alkyl (-R) group to a
benzene ring. Here the reagents used are alkyl halide in presence of anhydrous
AlCl3.

b) Friedel-Craft’s Acylation reaction: It is the introduction of acyl (-CO-R) group to a

benzene ring. Here the reagents used are acyl halide in presence of anhydrous
AlCl3.

5. Benzene on treatment with excess of chlorine in the presence of anhydrous AlCl3 in

dark to form hexachlorobenzene (C6Cl6).

II) Addition Reactions

1. Addition of H2: Benzene add hydrogen in presence of nickel catalyst at high
temperature and pressure to form cyclohexane.

2. Addition of halogen: Benzene adds chlorine in presence of uv light or at 500K to form

benzene hexachloride (BHC). It is also known as Gammaxane or Lindane or 666.

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Mechanism of Electrophilic substitution reactions

Electrophilic substitution reactions proceed through three steps: (a) Generation of the eletrophile (b)
Formation of carbocation intermediate (c) Removal of proton from the carbocation intermediate.
(a) Generation of the Electrophile: In chlorination, alkylation and acylation of benzene, anhydrous
AlCl3 helps in the generation of the electrophile Cl+(chloronium ion) , R+ (carbocation), RCO+
(acylium ion) respectively by combining with the attacking reagent.

In the case of nitration, the electrophile, nitronium ion (NO2+) is produced by the transfer of a proton
(from sulphuric acid) to nitric acid in the following manner:

(b) Formation of Carbocation (arenium ion):

Attack of electrophile results in the formation of σ-complex or arenium ion.

The arenium ion gets stabilised by resonance:

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(c) Removal of proton: To restore the aromatic character, σ -complex releases proton.

Directive influence of a functional group in mono-substituted benzene

When monosubstituted benzene undergoes further substitution, two types of
products are formed - either ortho and para products or meta product. This behaviour
depends on the nature of the substituent already present in the benzene ring. This is
known as directive influence of substituents.
Based on the directive influence, there are two types of substituents – ortho and para directing groups
and meta directing groups.
1. Ortho and para directing groups: The groups which direct the incoming group to ortho and
para positions are called ortho and para directing groups.
Example for such groups are -X, –OH, –NH2, –NHR, -NHCOCH3, –OCH3, –CH3, –C2H5 etc.
Generally, ortho-para directing groups are activating groups, since they increases the electron density
on benzene ring. Or, they activate the benzene ring for the attack by an electrophile.
Halogens are deactivating eventhough they are ortho-para directing. This is because of their strong –I
effect.
2. Meta direcing groups: The groups which direct the incoming group to meta position are
called meta directing groups. They are generally deactivating groups, since they reduces the electron
density on benzene ring.
Examples are –NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H, etc.
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Q1) An alkene on ozonolysis followed by reduction of the ozonide formed with zinc and
water gave a mixture of ethanal and methanal. Identify the alkene. Illustrate the
above mentioned reaction using the chemical equation.
Ans: Propene

Q2) Draw the cis and trans isomers of the following compound: C2H5-C(CH3) = C(CH3)-
C2H5.
Ans:

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