1 SOME BASIC CONCEPTS OF CHEMISTRY

2 ATOMIC STRUCTURE

3 CLASSIFICATION OF ELEMENTS AND PERIODICITY

4 CHEMICAL BONDING AND MOLECULAR STRUCTURE

5 THERMODYNAMICS

6 EQUILIBRIUM

7 REDOX REACTIONS

8 ORGANIC CHEMISTRY- SOME BASIC PRINCIPLES

9 HYDROCARBONS

UNIT 1: SOME BASIC CONCEPTS OF CHEMISTRY

Introduction:

This unit includes the classification of matter along with different laws of formation of
substances, significance of atomic mass, molecular mass and formula mass and mole concept
with brief introduction to the different methods for expressing the concentration of solutions ,

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computation of empirical and molecular formulae of compounds. This chapter brings about the
importance of chemistry in different fields of life by knowing different kinds of materials and their
composition.

Concept map: Chemistry

Importance of Matter and its Laws of Atomic mass Empirical and Expressing
Chemistry behavior Chemical and molecular molecular concentration
combination mass formula

Importance & scope of chemistry: The different fields in which chemistry plays its role are:

• Chemistry plays an important role in all aspects of life.

• Chemical principles are important in diverse areas such as weather patterns, functioning
of brain and operation of a computer
• Chemical industries manufacturing fertilizer, alkalis, acids, salts, dyes, polymers, drugs,
soaps, detergents, metals, alloys, and other inorganic and organic chemicals, including
new materials, contribute in a big way to the national economy.
• Chemistry plays an important role in meeting human needs for food, health care product
and other materials aimed at improving the quality of life.
• Many life saving drugs such as cisplatin and taxol, are effective in cancer therapy and ATZ
(Azidothymidine) used for helping AIDS victims, have been isolated from plant an a animal
sources or prepared by synthetic methods.
Laws of chemical combination:

Law of Conservation of Mass: Antoine Lavoisier proposed the Law of Conservation of

Mass. “It states that matter can neither be created nor destroyed”. In other words, we can say
that during any physical or chemical change, the total mass of reactants is equal to the total
mass of products.

Law of definite proportions: Joseph Proust proposed that a given compound always
contains exactly the same proportion of elements by weight.

Law of multiple proportions: Dalton proposed the law of multiple proportions.

According to this law if two elements can combine to form more than one compound, the mass
of one element that combines with the fixed mass of the other element is in the ratio of small
whole numbers.

Gay Lussac’s Law of gaseous volumes: When gases combine or are produced in a
chemical reaction they do so in a simple ratio by volume, provided all the gases are at same
temperature and pressure.

Avogadro Law: At the same temperature and pressure, equal volumes of gases contain
equal number of molecules. The number 6.022 × 1023 is called Avogadro’s constant or
Avogadro’s number.

Dalton’s atomic theory: The main postulates of Dalton’s theory are:

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 ➢ Matter consists of indivisible atoms.

➢ All the atoms of a given element have identical properties including identical
mass. Atoms of different elements differ in mass.

➢ Compounds are formed when atoms of different elements combine in a fixed

ratio.

➢ Chemical reactions involve reorganization of atoms. These are neither created

nor destroyed in a chemical reaction.

Concepts of elements, atoms, molecules, compounds and mixture:

Element: An element is defined as a pure substance that contains only one kind of atoms.
(e. g.) Carbon, sulphur, iron, lead, gold etc.

Atom: The smallest portion of a substance which may or may not have independent existence.
(e.g.) carbon, iron etc.

Molecule: The smallest portion of a substance which is capable of independent

existence.(e.g.) carbon dioxide, sulphur dioxide etc.

Compound: A compound is formed by the combination of two or more elements combined

together in a fixed ratio by mass.

(e.g.) carbon dioxide, water etc.

Mixture: a mixture is formed by the combination of two or more substances in any ratio. e.g.
alloys, air etc.

Types of Mixture: Homogenous mixtures are those in which components completely mix with
each other to make a uniform composition. e.g. air Heterogeneous mixtures are not uniform,
and their components can be separated through physical methods.

Atomic and molecular masses:

Atomic mass: Average relative mass of an atom of an element as compared with the mass of
a carbon atom taken as 12 amu.

Atomic mass expressed in grams is called gram atomic mass e.g. gram atomic mass of
nitrogen is 14g.

Molecular mass: Average relative mass of a molecule as compared with the mass of a
carbon atom taken as 12 amu. Molecular mass is calculated by the sum of the atomic masses
of all the elements present in a molecule. Molecular mass expressed in grams is called gram
molecular mass. e. g. molecular mass of methane (CH4) is 16.043g (12.011 g + 4x1.008
g=16.043g).

Mole concept and molar mass: One mole is the amount of a substance that contains as
many particles or entities as there are atoms in exactly 12 g (or 0.012 kg) of the 12C. A mole is a

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collection of 6.022 × 1023 particles. The mass of one mole of a substance in grams is called its
molar mass.

Following relations given below can be summarized

Formula of mole
Formula of moles:
Gram atomic mass or
gram molecular mass Given mass (W)
1. No. of moles =
Molar mass (M)

Given number
1Mole 2. No of moles =
Avogadro’s Number (NA)
6.022x1023particles 22.4L at STP

Percentage composition:
Percentage composition of a compound refers to the amount of various constituent
elements present per hundred parts by mass of the substance.

e.g. In ethanol there is 52.14 % C, 13.13 % H and 34.73 % of oxygen by mass

Empirical & Molecular Formula:

An empirical formula represents the simplest whole number ratio of various

atoms present in a compound.

Molecular formula shows the exact number of different types of atoms present in
a molecule of a compound.e.g. The molecular formula of glucose is C6H12O6 and empirical
formula is CH2O. If the mass per cent of various elements present in a compound is known,
its empirical formula can be determined.

Molecular formula = n x (Empirical formula)

where n is a simple number and may have values 1, 2, 3….

Following steps should be followed to determine empirical formula of the compound

Step 1: Conversion of mass per cent of various elements into grams.

Step 2: Convert mass obtained in step1 into number of moles

Step 3: Divide the mole value obtained in step 2 by the smallest mole value (out of the mole
value of various elements calculated)

Step 4: In case the ratios are not whole numbers, then they may into whole number by be
converted multiplying by the suitable coefficient.

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Step 5: Write empirical formula by mentioning the numbers after writing the symbols of
respective elements.

Stoichiometry and stoichiometric calculations :

The Stoichiometry deals with the calculation of masses of the reactants and
products involved in a reaction. It also helps us in identifying limiting reagents.

Problem: Calculate the amount of water(g) produced by the combustion of 16g of methane.

Solution:

Limiting reagent: The reactant which completely consumed in a chemical reaction is

called limiting reagent.

Example: In a reaction A + B2 → AB2, Identify the limiting reagent, when 300 atoms of A and
200 molecules of B reacts together.

Answer: B is limiting reagent.

Reactions in solutions: Since majority of reactions in chemistry lab are carried out in
solutions therefore it is important to understand as how the amount of solute is expressed
when it is present in the form of a solution. The concentration of the solution can be
expressed in any of the following ways:

Mass percentage: the amount of substance (solute) present in 100 gram of solution is
known as mass percentage.

Molarity (M): Molarity is the number of moles of solute in per litre of solution. Unit is moles
per litre (moleL-1)

Molality (m): Molality is the number of moles of solute present in 1kg of solvent. Unit is moles
per Kilogram (moleKg-1)

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Mole fraction (X): it is the ratio of number of moles of a particular component to the total
number of moles of the solution. If nA and nB number of moles of A and B combine to form a
solution then mole fraction of a is given by:

XA + XB = 1(sum of mole fraction is unity)

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 UNIT 2: STRUCTURE OF ATOM

Introduction:
The existence of atoms has been proposed since the time of early Indian and Greek
philosophers (400 B.C.) who were of the view that atoms are the fundamental building blocks of
matter. According to them, the continued subdivisions of matter would ultimately yield atoms
which would not be further divisible.

Concepts:
• Developments leading to the Bohr’s Model of the atom.
• Bohr's model of atom.
• Limitation of Bohr's model of atom.
• Dual nature of matter.
• Heisenberg uncertainty Principle.
• Quantum mechanical model of atom.
• Concept of orbital.
• Shapes of Atomic orbitals.
• Quantum numbers.
• Electronic Configuration of elements.
• Stability of half filled and fully filled orbitals.

Developments leading to the Bohr’s Model of the atom:

Dual nature of electromagnetic radiations: The electromagnetic radiations show wave
nature as revealed by James Maxwell. The electromagnetic radiations are oscillating electric &
magnetic fields produced by oscillating charged particles. These fields oscillate perpendicular to
each other & to the direction of propagation of light. These do not require a medium for
transmission. Just as in other waves they are characterized by:

a) Wavelength: Distance between two crest or trough in the wave which are in the same
phase. (SI unit is m). Represented by λ
b) Frequency: No. of waves that pass a given point in one second. (SI unit Hz or s—1)
Represented by
c) Wave number: It is the no. of wavelengths per unit length. It is the reciprocal of
wavelength. (SI unit is m-1) Represented by = 1/λ
d) Velocity: Velocity of all types of electromagnetic radiations is constant in air/ vacuum.
Represented by c. c = 3 x 108m/s
c = ʋλ

E = hʋ =
Particle Nature of Electromagnetic Radiation:
Planck’s Quantum Theory:
Some of the experimental phenomenon such as diffraction and interference can be
explained by the wave nature of the electromagnetic radiation. However, following are some of
the observations which could not be explained with the help of even the electromagnetic theory
of 19th century physics (known as classical physics):
(i) The nature of emission of radiation from hot bodies (black -body radiation)
(ii) Ejection of electrons from metal surface when radiation strikes it (photoelectric effect)
(iii) Variation of heat capacity of solids as a function of temperature

(a) Black Body Radiation: The ideal body which emits or absorbs radiations of all
frequencies is called a black body & the radiation emitted by such a body is called Black body
radiation.

Graph of intensity of radiation emitted versus wavelength of radiation emitted by a black

body at two different temperatures is given below:

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

wavelength, reaches a maximum value at a given wavelength and then starts decreasing with
further decrease of wavelength.The above experimental results cannot be explained
satisfactorily on the basis of the wave theory of light. Planck suggested that atoms and
molecules could emit (or absorb) energy only in discrete quantities and not in a continuous
manner, a belief popular at that time. Planck gave the name quantum to the smallest quantity of
energy that can be emitted or absorbed in the form of electromagnetic radiation. The small
particle of quantum is called Photon and it’s energy is given by:

E = hʋ =

(b) Photoelectric effect: This is the phenomenon where electrons are emitted when certain
metals like K, Rb, and Cs are exposed to a beam of light.

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Salient features of photoelectric effect:

• The electrons are ejected from the metal surface as soon as the beam of light strikes the
metal.
• No: of electrons ejected is proportional to the intensity of incident light.
• Each metal requires a minimum frequency of radiation (called threshold frequency) ʋo
below which photo electric effect is not observed.
• Kinetic energy of the photoelectrons depends upon the energy of the incident photon.
• hʋ = hʋo + 1/2mv2
• Work Function of the metal is the minimum energy required by the metal to emit
photoelectrons.

Bohr’s model for hydrogen atom :

Bohr proposed a quantum mechanical model of the atom, to overcome the objections of
Rutherford’s model and to explain the hydrogen spectrum. The important postulates on which
Bohr’s model is based are the follows:

1. An electron in the hydrogen atom can move around the nucleus in a circular path of fixed
radius and energy. These paths are called orbits or energy levels. These orbits are arranged
concentrically around the nucleus.

2 As long as an electron remains in a particular orbit, it does not lose or gain energy and
its energy remains constant.

3 When transition occurs between two stationary states that differ in energy, the
frequency of the radiation absorbed or emitted can be calculated

4 An electron can move only in those orbits for which its angular momentum is an
integral multiple of h/2
mvr = nh/2 n = 1,2,3,4…………….

Limitations of Bohr’s model of atom:

a. Bohr‘s model failed to account for the finer details of the hydrogen spectrum.
b. Bohr‘s model was also unable to explain spectrum of atoms containing more than
one electron.

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 c. Bohr‘s model couldn’t explain the Zeeman effect and stark effect.
d. It ignores the dual behaviour of matter.
e. It contradicts Heisenberg‘s uncertainty principle.

Dual behavior of matter: de Broglie proposed that matter exhibits dual behaviour i.e.
matter shows both particle and wave nature. For any particle
λ=

Heisenberg’s uncertainty principle: It states that it is impossible to determine

simultaneously, the exact position and exact momentum (or velocity) of an electron. The product
of their uncertainties is always equal to or greater than h/4π.
Mathematically ∆x. ∆p ≥ Where, ∆x is the uncertainty in position
∆p is the uncertainty in momentum
Significance of uncertainty principle: The effect of Heisenberg Uncertainty Principle is
significant only for motion of microscopic objects and is negligible for that of macroscopic
objects.
Quantum mechanical model of atom: Quantum mechanics is a theoretical science that
deals with the study of the motions of the microscopic objects that have both observable wave
like and particle like properties. It specifies the laws of motion that these objects obey.
Schrödinger wave equation is written as
H =E where H is a mathematical operator called Hamiltonian.
Important Features of the Quantum Mechanical Model of Atom:
• The energy of electrons in atoms is quantized.
• The existence of quantized electronic energy levels is a direct result of the wave like
properties of electrons and is allowed solutions of Schrödinger wave equation.
• Both the exact position and exact velocity of an electron in an atom cannot be
determined simultaneously (Heisenberg uncertainty principle).
• An atomic orbital is the wave function for an electron in an atom.
• The probability of finding an electron at a point within an atom is proportional to the
square of the orbital wave function i.e., | |2 at that point. | |2 is known as probability
density and is always positive.

Orbital: The three dimensional region or space around the nucleus where the probability of
finding an electron is maximum is called an orbital.
Quantum numbers: These are a set of four quantum numbers which gives the complete
information about the electron in atom i.e. the energy, size, shape and orientation of an orbital
as well as the spinning motion of an electron .
Types of quantum numbers:
(i) Principal quantum no.(n)
(ii) Azimuthal quantum no.(l) or Orbital angular momentum or subsidiary quantum number
(iii) Magnetic quantum no. (ml)
(iv) Spin quantum no. (ms)

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 Principal Azimuthal Sub shell Magnetic Electron Total
quantum quantum designation quantum number spin number
number (n) number (l) or magnetic quantum of orbital
orbital quantum number (ms) in shell
number (ml)
Number of Sub shell s, p , d and f Number Orientation
shell and size of Orbitals of the spin of n2
electron
1 0 1s 0 1
0 2s 0
2 4
1 2p +1,0, -1
0 3s 0
3 1 3p +1,0, -1 Clockwise or 9
2 3d +2,+1,0,-1,-2 anti clock
0 4s 0 wise
1 4p +1,0, -1
4 16
2 4d +2,+1,0,-1,-2
3 4f +3,+2,+1,0,-1,-2,-3

Difference between orbit and orbital :

Orbit
It is defined as the definite circular path
through which electron revolves around the
nucleus.
It is two dimensional path
The position and velocity of moving electron in
an orbit can be calculated simultaneously with
great accuracy
Maximum no. of electron that can be present
in an orbit = 2n2
Orbital
The three dimensional region or space
around the nucleus where the probability of
finding an electron is maximum is called an
orbital.
It is three dimension region
The position and velocity of moving electron
in an orbit can’t be calculated
simultaneously with great accuracy
Maximum 2 electrons can be present in an
orbital

Shapes of Atomic orbitals :

Shapes of d orbitals:

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Rules for writing the electronic configuration:
Aufbau principle: In the ground state of the atoms, the orbital’s are filled in order of
their increasing energies. In other word electron first occupy the lowest energy orbital Available
to them.
The increasing order of the energies
the orbital’s is as follows:
1s<2s< 2p< 3s< 3p< 4s< 3d< 4p<
5s< 4d< 5p< 4f< 5d< 6p< 7s...
The order in which the orbital’s are filled
is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d,
5p, 4f, 5d, 6p, 7s...
( n + l ) rule:
• Orbital’s with lower value of ( n + l )
have lower energy.
• If two orbital’s have the same value
of (n + l) then orbital with lower
value of n will have lower energy.
e.g n+l for
n l
4s 4 0
3d 3 2
Hence according to n+l rule, for 4s is 4 while 3d is 5.
Therefore 4s < 3d

Pauli’s Exclusion Principle: No two electrons in an atom can have the same set of four
quantum numbers. Only two electrons may exist in the same orbital and these electrons
must have opposite spin. e.g. He (2) = 1s2
for first electron n = 1 , l = 0 ml = 0 , ms = +1/2
for second electron n = 1 , l = 0 , ml = 0 , ms = - ½
Hund’s rule of maximum multiplicity: “pairing of electrons in the orbital’s belonging
to the same sub shell (p, d or f) does not take place until each orbital belonging to that
sub shell has got one electron each i.e., it is singly occupied.
e.g. N(7) = 1s22s22p3

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Electronic configuration of atom: The distribution of electrons into orbitals of an atom is
called its electronic configuration. The electronic configuration of different atoms can be
represented in two ways.
Some examples:

Stability of completely filled and half filled sub shells :

• Symmetrical distribution of electrons: The completely filled or half filled sub-

shells have symmetrical distribution of electrons in them and are more stable.

• Exchange energy: The two or more electrons with the same spin present in the
degenerate orbitals of a sub-shell can exchange their position and the energy
released due to this exchange is called exchange energy. The number of exchanges
is maximum when the sub shell is either half filled or completely filled. As a result the
exchange energy is maximum and so is the stability.

Possible exchanges for d5 electronic configuration

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 UNIT 3: CLASSIFICATION OF ELEMENTS AND PERIODICITY
IN PROPERTIES
Introduction:
This unit includes the concept of grouping elements in accordance to their properties led
to the development of Periodic Table and to recognize the periodic trends in physical and
chemical properties of elements. Further we will be able to know name the elements with Z
>100 according to IUPAC

Important points:

Modern periodic table: Henry Moseley observed regularities in the characteristic X-ray
spectra of the elements. A plot of √v (where v is frequency of X-rays emitted) against atomic
number (Z ) gave a straight line and not the plot of √v vs atomic mass. He thereby showed that
the atomic number is a more fundamental property of an element than its atomic mass.

Modern Periodic Law: The physical and chemical properties of the elements are periodic
functions of their atomic number.

Groups and Periods: The horizontal rows are called periods and the vertical columns are
called groups. Elements having similar outer electronic configurations in their atoms are
arranged in vertical columns, referred to as groups or families. There are 18 groups and 7
periods in modern periodic table.
The period number corresponds to the highest principal quantum number(n) of the
elements in the period. The first period contains 2 elements. The subsequent periods consists of
8, 8, 18, 18 and 32 elements, respectively. The seventh period is incomplete and like the sixth
period would have a theoretical maximum of 32 elements

Naming of elements atomic no. >100: The name is derived directly from the atomic
number of the element using the following Latin numerical roots:
Number 0 1 2 3 4 5 6 7 8 9
Root nil un bi tri quad pent hex sept oct enn
symbol 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. Example: Atomic no. 105 will be named as Unnilpentium (Unp).
General properties of different block elements:
Properties s-block p-block d-block f-block elements remarks
elements elements elements
Electronic ns1,2 ns2 np1-6 (n-1) d1-10 (n-2)f1-14 (n-1)d0,1ns2 f-block elements
configuration ns0-2 shows some
exceptions
Position Group-1,2 Group-13- Group-3-12 Lanthanoids & f-block elements
18 Actinoids are called(inner
transition
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 elements
Nature All metals Metals, non All metals Metals and manmade Actinoids are
except metals and elements radioactive
hydrogen metalloids
Reactivity Increase Increase Reactivity in Reactivity in between Highly electro
down the across the between s s block and p block positive metals
group period block and p and highly
block electronegative
non metals are
reactive
Bonding Mostly ionic Mostly Covalent in Covalent in higher Ionic
covalent higher oxidation state compounds has
oxidation higher melting
state points
Ionization Low High Higher than Higher than s block ------
enthalpy s block elements
elements
Flame colour Show flame No flame Some gives No flame colour -------
colour colour flame colour
Inert pair effect Do not Show inert Do not Do not show inert pair Stability of lower
show inert pair effect show inert effect ox. state
pair effect pair effect increases down
the group for p-
block elements

Periodic trends in modern periodic table :

Properties Definition Units Trend
Down the Across the
group period
Atomic radii Distance between the Pm increase decrease
outermost valence shell (picometer )  
and nucleus in an atom
Ionic radius Distance between the Pm increase decrease
outermost valence shell (picometer)  
and nucleus in an ion
Ionisation Energy required to remove decrease increase
Enthalpy(ΔiH) electron from an isolated kJmol-1  
gaseous atom in ground
state
Electron gain Enthalpy change involved positive for noble decrease increase
enthalpy (ΔegH ) when electron added to a gases  
neutral gaseous atom to
convert into negative ion
Electronegativity It measures the ability of F is having the decrease increase
an atom in a chemical highest ability to  
compound to attract shared attract electrons
electrons to itself was assigned
arbitrary value of 4
Non Metallic The tendency of an atom to Directly decrease increase
character accept electron to form proportional to  
anion electronegativity

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 Anomalous properties:
The 2nd period elements of each group (i.e. Li, Be, B, C, N, O, F) shows different
properties than the other elements of its own group is called anomalous properties. e. g . Li3N
exists but K3N does not exist. NCl5 does not exist but PCl5 can exist.
The anomalous property is due to the following reasons:
• Small size
• High electronegativity
• Absence of d-subshell
• High ionisation enthalpy
• Presence of multiple bonding to form pл – pл multiple bonds to itself (e.g., C = C, C C, N =
N, C ≡ N) and to other second period elements
Points to remember:
1. In the first transition series the atomic size slightly decreases from Sc to Mn because
effect of effective nuclear charge is stronger than the shielding effect. The atomic size
from Fe to Ni remains almost the same because both the effects balance each other.
Within a given group atomic radius increases down the group. This is due to the increase in
number of shells.
2. Isoelectronic species: Ions which contain the same number of electrons are called
isoelectronic species. For example, O2–, F–, Na+ and Mg2+ have the same number of electrons
(10). Among isoelectronic species, the one with the larger positive nuclear charge will have a
smaller radius.
3. The second ionization enthalpy will be higher than the first ionization enthalpy because it is
more difficult to remove an electron from a positively charged ion than from a neutral atom. In
the same way the third ionization enthalpy will be higher than the second and so on. High
Ionisation energy of noble gases which have closed electron shells and very stable electron
configurations. On the other hand, minima occur at the alkali metals and their low ionization
enthalpies can be correlated with their high reactivity.

1. Factors which influence ionization Enthalpy (I.E.)

i) Atomic size: The larger the size of the atom, the smaller the I.E.

ii) Effective nuclear charge: The greater the effective charge on the nucleus of an atom, the
more difficult it would be to remove an electron from the atom because electrostatic force of
attraction between the nucleus and the outermost electron increases. So greater energy will be
required to remove the electron.

iii) Penetration effect of orbital’s: The order of energy required to remove electron from s, p,
d-and f-orbital’s of a shell is s>p>d>f.

iv) Shielding or screening effect: Screening effect results in decrease of force of attraction
between the nucleus and the outermost electron and lesser energy is required to separate the
electron. Thus the value of I.E. decreases down the group.

v) Stability of half-filled and fully-filled orbitals: According to Hund's rule the stability of half
filled or completely filled degenerate orbitals is comparatively high. So comparatively more
energy is required to remove the electron from such atoms.

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5. Factors affecting the magnitude of Electron gain enthalpy
i) Atomic size – In general electron affinity value decreases with the increasing atomic radius
because electrostatic force of attraction decreases between the electron being added and the
atomic nucleus due to increase of distance between them.
ii) Effective nuclear charge – Electron affinity value of the element increase as the effective
nuclear charge on the atomic nucleus increases because electrostatic force of attraction
between the electrons being added and the nucleus increases. As the electrostatic force of
attraction increases, amount of energy released is more.
iii) Screening or Shielding effect – Electron affinity value of the elements decreases with the
increasing shielding or screening effect. The shielding effect between the outer electrons and
the nucleus increases as the number of electrons increases in the inner shells.

6. Factors affecting the magnitude of electronegativity:

i) Atomic radius: As the atomic radius of the element increases the electronegativity value
decreases.
ii) Effective nuclear charge: The electronegativity value increases as the effective nuclear
charge on the atomic nucleus increases.
iii) Oxidation state of the atom: The electronegativity value increases as the oxidation state
(i.e. the number of positive charge) of the atom increases.
iv) Hybridisation state of an atom in a molecule: If the s- character in the hybridisation state
of the atom increases, electronegativity also increases

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18
 UNIT 4: CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Introduction:
Matter is made up of atoms. Atoms are usually not capable to exist freely. A group of
atoms existing together as one species and having characteristic properties is called a
molecule. e.g., H2, O2, P4, S8, H2O. Obviously, there must be some force which holds these
atoms together within the molecules.

Why do atoms combine?

To answer such question different theories and concepts have been put forward from
time to time. These are:
1. Kossel-Lewis approach
2. Valence Shell Electron Pair Repulsion (VSEPR) Theory
3. Valence Bond (VB) Theory
4. Molecular Orbital (MO) Theory.
Lewis Approach to Chemical Bonding:

Lewis pictured the atom in terms of a positively charged Kernel (the nucleus plus the
inner electrons) and the outer shell that could accommodate a maximum of eight electrons.
The atoms of different elements combine with each other in order to complete their
respective octets (i.e., 8 electrons in their outermost shell) or duplet (i.e., outermost shell having
2 electrons) in case of H, Li and Be to attain stable nearest noble gas configuration.

Mode of chemical combination

This can occur in two ways:

1. By complete transference of one or more electrons from one atom to another, the
chemical bond formed is termed as electrovalent bond or ionic bond.

2. By sharing of electrons the bond formed is called covalent bond.

Lewis symbols: The outer shell electrons are shown as dots surrounding the symbol of
the atom. These symbols are known as Lewis symbols or electron dot symbols. These symbols
ignore the inner shell electrons. A few examples are given below :

Kossel approach of chemical bonding:

When a bond is formed by complete transference of electrons from one atom to another
to acquire the stable nearest noble gas configuration, the bond formed is called ionic bond or
electrovalent bond.

Explanation of Ionic Bond: Atoms are electrically neutral. Therefore, they possess
equal number of protons and electrons. On losing an electron, an atom becomes positively
charged since now the number of protons exceeds the number of electrons.

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 A → A+ + e-

On the other hand, in case of atom, gaining the electron, the number of electrons
exceeds the number of protons and thus the atom becomes negatively charged.

B + e- → B-

The oppositely charged particles formed above attract each other by electrostatic forces
of attraction. The bond thus formed is known as electrovalent or ionic bond.

Electrovalency:

The number of electrons lost or gained during the formation of an electrovalent linkage is
termed as the electrovalency of the element.

For example, sodium and calcium lost 1 and 2 electrons respectively and so their
valencies are 1 and 2. Similarly, chlorine and oxygen gain 1 and 2 electrons respectively, so
they possess an electrovalency of 1 and 2. In other words, valency is equal to the charge on the
ion.

Octet rule: According to Kossel and Lewis atoms can combine either by transfer of valence
electrons or by sharing of electrons in order to have an octet in their valence shell. This is
known as octet rule.

Covalent bond: Langmuir (1919) refined the Lewis postulations by abandoning the idea
of the stationary cubical arrangement of the octet, and by introducing the term covalent bond.
The bond formed between the two atoms by mutual sharing of electrons between them so as to
complete their octets or duplets [in case of elements having only one shell] is called covalent
bond or covalent linkage and the number of electrons contributed by each atom is known as
covalency. So Lewis-Langmuir theory can be understood by considering the formation of
following molecules:

If two atoms share one, two and three electron pairs the convalent bond between them is
called single, double and triple covalent bond.

Lewis representation of simple molecules (the Lewis structure):

Formal charge:

20
 [ total no of (1/2) [total no
Formal charge [total no of
nonbonding bonding
(F.C.) on an atom valence –
= (lone pairs) – (shared)
in a Lewis electrons in
electrons] electrons]
structure the free atom]

Significance of formal charge: The main advantage of the calculation of formal charges is
that it helps to select the most stable structure, i.e., the one with least energy out of the different
possible Lewis structures. The most stable is the one which has the lowest formal charges on
the atoms.

Limitation of the octet rule:

There are three types of exceptions to the octet rule.
1- The incomplete octet of the central atom. e.g: LiCl, BeH2 and BCl3.
2- Odd-electron molecules. e.g. : NO, NO2
3- The expanded octet. e.g. : PF5, SF6, H2SO4
4- Although Xe has stable configuration (octet of electrons) yet it form
number of compounds. e.g. XeF2, XeOF2 etc.
5- Give no idea about shape of molecule.

Factors governing the formation of ionic bonds:

Ionisation Enthalpy: It is clear that lesser the ionisation enthalpy, easier will be the removal of
an electron, i.e., formation of a positive ion and hence greater the chances of formation of an
ionic bond. Ionisation enthalpy (I.E.) of alkali metals (i.e., group I elements) is low, hence they
have more tendency to form positive ions.

Electron Gain Enthalpy: Higher is the negative electron gain enthalpy, more affinity for
incoming electrons, more is the energy released and stable will be the negative ion produced.
Consequently, the probability of formation of ionic bond will be enhanced. Halogens possess
high negative value of electron gain enthalpy.

Lattice Enthalpy (Lattice Energy): The Lattice Enthalpy of an ionic solid is defined as the
energy required to completely separate one mole of a solid ionic compound into gaseous
constituent ions.
For example, the lattice enthalpy of NaCl is 788 kJ mol–1. This means that 788 kJ of
energy is required to separate one mole of solid NaCl into one mole of Na+ (g) and one mole of
Cl– (g) to an infinite distance.

Bond Parameters:

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

Factors affecting bond length:

(i) Size of the atoms: The bond length increases with increase in the size of the atoms.
For example, bond lengths of H–X are in the order: HI > HBr > HCl > HF

21
 (ii) Multiplicity of bond : The bond length decreases with the multiplicity of the bond.
Thus, bond length of carbon-carbon bonds are in the order: CΞC <C=C<C–C

(iii) Type of hybridisation : s orbital is smaller in size, greater the s- character, shorter
is the hybrid orbital and hence shorter is the bond length. For example,

Bond lengths: sp3 C–H > sp2 C–H > sp C–H

s-character: (25%) (33%) (50%)

Bond Enthalpy: The amount of energy required to break one mole of bonds of a particular
type so as to separate them into gaseous atoms is called bond dissociation enthalpy or simply
bond enthalpy.

Factors affecting Bond Enthalpy

(i) Size of the atoms: Greater the size of the atoms, greater is the bond length and
less is the bond dissociation enthalpy, i.e., less is the bond strength.

(ii) Multiplicity of bonds: For the bond between the same two atoms, greater is the
multiplicity of the bond, greater is the bond dissociation enthalpy. This is firstly because atoms
come closer and secondly, the number of bonds to be broken is more. For example, bond
dissociation enthalpies of H2, O2 and N2 are in the order: H–H < O = O < NΞ N

(iii) Number of lone pairs of electrons present: Greater the number of lone pairs of
electrons present on the bonded atoms greater is the repulsion between the atoms and hence
less is the bond dissociation enthalpy.

Bond angle: It is defined as the angle between the orbitals containing bonding electron pairs
around the central atom in a molecule/complex ion.

Bond order: In the Lewis representation of a molecule or ion, the number of bonds present
between two atoms is called bond order. For example, the bond orders of a few molecules are
given below:

Molecule: H—H O=O NΞN CΞO

Bond order: 1 2 3 3

Isoelectronic molecules and ions have identical bond orders

Resonance structures:
According to the concept of resonance, whenever a single Lewis structure cannot
describe a molecule accurately, a number of structures with similar energy, positions of nuclei,
bonding and non-bonding pairs of electrons are taken as the canonical structures of the hybrid
which describes the molecule accurately.

22
 Thus the energy of the CO 3 2- resonance hybrid (D) is lower than any of the three
canonical forms A, B and C

Note:-
• Resonance stabilizes the molecule as the energy of the resonance hybrid is less than
the energy of any single canonical structure.
• Resonance averages the bond characteristics as a whole.

Dipole moment:
A molecule with positive and negative charge centres in equilibrium is called as dipole
and is characterised by possessing a quantity dipole moment (µ) defined as the product of the
magnitude of charge (q) and the distance (r) separating the centres of +ve and –ve charges. Its
direction is from +ve end to – ve end.

µ=Q×r

Dipole moment is usually expressed in Debye units (D). 1 D = 3.33564 X 10-30 cm

The dipole moment of a molecule is the vector sum of the dipole moments of various
bonds these bonds have some spatial arrangements in molecules so dipole moments of
molecule help us predicting the shape of molecule.

For example CO2 has zero dipole moment, mean linear shape and H2O which is also
triatomic molecule has net dipole moment µ=1.85 D not has linear shape but angular shape.

CCl4, CH4 have zero dipole moment, mean symmetrical tetrahedral structure etc.

Fajan’s Rule:

Cation attracts the electron cloud of anion towards itself and thereby increasing the
electronic charge density between the two hence has partial covalent character in ionic bond.

• The smaller the size of the cation and the larger the size of the anion, the greater the
covalent character of an ionic bond. e.g. LiI

23
• The greater the charge on the cation, the greater the covalent character of the ionic
bond. e.g. AlCl3
• For cations of the same size and charge, the one, with electronic configuration (n-1)dn
nso, is more polarising than the one with a noble gas configuration, ns2 np6, typical of alkali and
alkaline earth metal cations. e.g. Hg2+ is more polarising than Ca2+.

Valence shell electron pair repulsion theory:

The first simple theory that was put forward to explain the shapes of molecules is known
as Valence Shell Electron Pair Repulsion (VSEPR) theory. This theory was given by Sidgwick
and Powell in 1940 and was further improved by Nyholm and Gillespie in 1957.

Postulates of VSEPR theory:

• The shape of a molecule depends upon the number of valence shell electron pairs
(bonded or nonbonded) around the central atom.
• Pairs of electrons in the valence shell repel one another.
• These pairs of electrons tend to occupy such positions in space that minimise repulsion
and thus maximize distance between them.
• The valence shell is taken as a sphere with the electron pairs localising on the spherical
surface at maximum distance from one another.
• A multiple bond is treated as a single electron pair.
• Where two or more resonance structures can represent a molecule, the VSEPR model is
applicable to any such structure.
Lone pair (lp) - Lone pair (lp) > Lone pair (lp) - Bond pair (bp) > Bond pair (bp) -Bond pair
(bp)
The electron pairs surrounding the central atom repel one another and move so far apart from
one another that there are no further repulsions between them. As a result, the molecule has
minimum energy and maximum stability.

24
25
Valence bond theory:

Valence bond theory was introduced by Heitler and London (1927) and developed
further by Pauling and others.
26
Valence bond theory is based on:
• Knowledge of atomic orbitals,
• Electronic configurations of elements
• The overlap criteria of atomic orbitals,
• The hybridization of atomic orbitals and
• The principles of variation and superposition.

Orbital overlapping concept:

Partial merging of atomic orbitals is called overlapping of atomic orbitals which results in
the pairing of electrons having opposite spin. The extent of overlap decides the strength of a
covalent bond
Directional Properties of Bonds:

The valence bond theory explains the shape, the formation and directional properties of
bonds in polyatomic molecules like CH4, NH3 and H2O, etc. in terms of overlap and hybridisation
of atomic orbitals.
OVERLAPPING OF ATOMIC ORBITALS:
Atomic orbital overlap does not give any idea about the directional characteristics of bonds
(geometrical shapes of molecule).

Types of overlapping and nature of covalent bonds:

Depending upon the type of overlapping, the covalent bonds are mainly of two types:

i) Sigma bond:
When a bond is formed between two atoms by the overlap of their atomic orbitals along the
inter nuclear axis (end to end or head on overlap), the bond formed is called sigma (σ) bond.

(i) s-s overlapping

(ii) s-p overlapping

(ii) p-p overlapping

27
ii) Pi (π) Bond:
Pi-bond is formed by lateral (sidewise) overlapping of p-orbitals, i.e., by overlapping of p-
orbitals in a direction at right angles to the inter nuclear axis (figure)

Comparison sigma and pi bonds:

Sigma Bond Pi Bond
(i) This bond is formed by overlap of (i) This is formed by sideway
orbitals along their internuclear axis (end overlapping of orbitals (lateral
to end overlap) overlapping).

(ii) This is formed by overlapping between (ii) This is formed by the overlap of p-p
s-s, s-p and p-p orbitals. orbitals only.

(iii) Overlapping is quite large and hence (iii) Overlapping is to a small extent.
sigma bond is a strong bond. Hence π-bond is a weak bond.

(iv) Electron cloud in this case is (iv) Electron cloud of π-bond is

symmetrical about the line joining the
two nuclei.
(v) Sigma bond consists of only one
electron cloud, symmetrical about the
inter nuclear axis.
unsymmetrical.
(v) Pi (π) bond consists of two electron
clouds, one above the plane of
atomic nuclei and the other below it.

(vi) Free rotation about a sigma-bond is (vi) Free rotation about π-bond is not
possible. possible.

Hybridisation:

Hybridisation is defined as the mixing of the atomic orbitals belonging to the same atom
but having slightly different energies so that a redistribution of energy takes place between them
resulting in the formation of new orbitals of equal energies and identical shapes. The new
orbitals thus formed are known as hybrid orbitals.

Salient features of hybridisation:

1. The number of hybrid orbitals is equal to the number of the atomic orbitals that get hybridised.
2. The hybridised orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
4. These hybrid orbitals are directed in space in some preferred direction to have minimum
repulsion between electron pairs and thus a stable arrangement. Therefore, the type of
hybridisation indicates the geometry of the molecules.

28
Conditions for hybridisation:
• The orbitals present in the valence shell of the atom are 29ybridized.
• The orbitals undergoing hybridisation should have almost equal energy.
• Promotion of electron is not essential condition prior to hybridisation.
• It is not necessary that only half filled orbitals participate in hybridisation. In some cases,
even filled orbitals of valence shell take part in hybridisation.

Type of Hybridisation:

Identification of Hybridisation of central atom:

Calculate the number of hybrid orbitals (X) to be formed by the central atom as follows :

X = ½ [VE + MA – C + A]

• MA = No. of monovalent atoms

• VE = No. of valence electrons around central atom
• C =No. of cation
• A = No. of an anion

If X=2 it means two hybrid orbitals are to be formed. Hence, hybridization is sp. If X=3, it
means three hybrid orbitals are to be formed. Hence, hybridization is sp2 and so on.

Molecular orbital theory:

There is another approach to chemical bonding known as molecular orbital theory (MOT)
developed by R.S Mulliken and F. Hund in 1932. The salient features of this theory are:

• The electrons in a molecule are present in the various molecular orbitals as the electrons
of atoms are present in the various atomic orbitals.
• The atomic orbitals of comparable energies and proper symmetry combine to form
molecular orbitals.

29
 • Molecular orbital is influenced by two or more nuclei depending upon the number of
atoms in the molecule. Thus, an atomic orbital is monocentric while a molecular orbital is
polycentric.
• The number of molecular orbital formed is equal to the number of combining atomic
orbitals. When two atomic orbitals combine, two molecular orbitals are formed. One is
known as bonding molecular orbital (lower energy level) while the other is called
antibonding molecular orbital ( high energy level).
• The electron probability distribution around a group of nuclei in a molecule is given by a
molecular orbital.
• The molecular orbitals like atomic orbitals are filled in accordance with the aufbau
principle obeying the Pauliís exclusion principle and the Hundís rule.

Conditions for atomic orbitals to form M.O.

• The combining A.O. should be of a comparable energy.

• The combining atomic orbitals must have the same symmetry about the molecular axis.
• The combining atomic orbitals must overlap to a large extent greater the overlap, stable
is the molecule formed.

Relative energies of M.O. and filling of electron

M.O Energy level diagram for O2, F2 and Ne M.O energy diagram for Li2, Be2, B2, C2 and
N2 molecule

The increasing order of energies of various molecular orbitals for O2 and F2 is given below :

The increasing order of energies of various molecular orbitals up to N2 is given below :

30
Bond order (B.O.) = (No. of electrons in BMO - No. of electrons in ABMO)/ 2

• Stability α Bond order

• Those with positive bond order are considered stable molecule while those with negative
bond order or zero bond order are unstable molecule.

If all the molecular orbitals in species are spin paired, the substance is diamagnetic.
But if one or more molecular orbitals are singly occupied it is paramagnetic.

Hydrogen bonding:Hydrogen bond can be defined as the attractive force which binds
hydrogen atom of one molecule with the electronegative atom (F, O or N) of anothermolecule.

As a result of hydrogen bonding, a H–atom links the two electronegative atoms

simultaneously, one by a covalent bond and the other by a hydrogen bond. Hence it is said to
form a hydrogen bridge. It is merely a strong electrostatic attractive forces and not a normal
chemical bond. It is very weak (strength about 2-10 K cal/mol).

Conditions for Hydrogen bonding

• The molecule must contain a highly electronegative atom linked to

H-atom. The higher the electronegativity more is the polarisation of the molecule.
• (b) The size of the electronegative atom should be small. The
smaller the size the greater is the electrostatic attraction.

Types of Hydrogen bonding

1. Intermolecular Hydrogen bonding:
When hydrogen bonding takes place between different molecules
of the same or different compounds, it is called intermolecular hydrogen bonding e.g.
HF, H2O, ROH (same compound) water-alcohol, water-ammonia (different compound)
etc.

2. Intramolecular hydrogen bonding:

The hydrogen bonding which takes place within a molecule itself. It takes
place in compounds containing two groups such that one group contain a H-atom linked to an
electronegative atom and the other group contains a highly electronegative atom linked to a
lesser electronegative atom. The bond is formed between the H atom of one group with the
more electronegative atom of the other group.

o-nitro phenol

31
Other examples of hybridisation:

sp3 hybridisation in ammonia (pyramidal) and water molecule (angular)

Octahedral geometry of SF6 molecule

32
 UNIT 6: CHEMICAL THERMODYNAMICS
Introduction
Why does heat flow from hot to cold bodies? why the air becomes thinner and colder at
higher altitudes? Why the Sun appears yellow whereas colder stars appear red and hotter stars
appear bluish-white? Why it is impossible to measure a temperature below -273 0C? Why there
is a maximum theoretical efficiency of a power generation unit which can never be exceeded no
matter what the design? Why high mass stars must ultimately collapse to form black-holes, and
much more? All the above questions can be answer through thermodynamics.

Thermodynamics:
It is the branch of science concerned with heat and temperature and their relation to
energy and work.
Thermodynamics is essentially the study of the internal motions of many body systems.
Terminology of Thermodynamics:
System: A specified part of the universe which is under investigation (experiments,
observations and their inference) is called system.
Surroundings: Part of the universe other than the system is known as surroundings.
The system and surrounding is separated by boundaries if boundary is allows the passage of
energy then named as isotherm and if does not allows the passage of energy then adiotherm
boundary.
Open system: A system which can exchange matter as well as energy with the surroundings is
called open system e.g. hot water in a beaker.
Closed system: A system which can exchange energy but not the matter with the surroundings
is called closed system e.g. hot water in a closed metallic container.
Isolated system: A system which can neither exchange matter nor energy with the
surroundings is called isolated system e.g. hot water in a well insulated thermos flask.
State of a system: State of the system may be defined as the condition of the system when its
observable properties have definite values. Such properties include temperature, pressure,
energy, enthalpy, entropy and free energy.
State functions or state variables: The properties which depend only on the state of the
system and remain independent of the method by which that state is achieved, are called state
variables. Some common state variables are temperature, volume, pressure and composition.
Extensive and intensive properties: The properties which depend upon the quantity of matter
present in system are called as extensive properties such as internal energy, heat capacity,
enthalpy, mass and volume etc.
The properties which are independent with the amount of substance are called as
intensive properties such as density, boiling point, melting point, specific heat capacity etc.
Microscopic and macroscopic properties: The system containing individual atom or molecule
is called as microscopic system and its properties as microscopic properties.
The system containing large number of chemical species such as atoms, or molecules or ions,
is called as macroscopic system. Its properties due to interaction of species are called as
macroscopic properties. Example- Pressure, volume, temperature etc.
Thermodynamics deals with macroscopic properties.

42
Thermodynamics scale of temperature: Kelvin is the SI unit of temperature, which is based
upon triple point of water. Triple point is a state of water at 0.01 ˚C temperature and 4.58 torr
pressure which is comprised by ice, liquid water and water vapour in equilibrium.
One Kelvin is equal to of triple point and its lowest point is zero Kelvin which is lowest
possible temperature and called as absolute zero temp.
In Celsius scale 0˚C is temperature of freezing point of water and 100˚C is boiling point of water
that is assigned on the basis of freezing point and boiling point of water.
Isothermal process: The thermodynamic process during which temperature remains constant
throughout the process are called as isothermal process (. )
Adiabatic Process: The thermodynamic process during which heat exchange between system
and surrounding is not possible (.

Isobaric process: The thermodynamic process occurring at constant pressure (. )

Isochoric process: The thermodynamics process occurring at constant volume. =0)

Cyclic process: The thermodynamic process having same initial and final state.
Reversible and irreversible process: The thermodynamics process occurring with very slow
rate in such a way that process remains in equilibrium with surrounding after each step; during
such process all state function remains constant. This type of state of system is also called as
‘quasi equilibrium’ state. For example removal of sand particles kept upon piston of a vessel
containing gas.
Heat, Work and Internal Energy
Heat: Heat is a form of energy which flows from region of high temperature to the region of low
temperature. For example if we take a piece of ice it gives us cold sensation due to transfer of
heat from body to the ice required for melting if ice.
If heat is absorbed by system then it will be positive and if evolved by the system then it will be
negative.
Work: If work is done by system then it will be negative and if work is done on the system then
it will be positive. Work is of following two types.
Work done in irreversible isothermal process: Let us consider a system having volume V1 at
constant pressure P expands or compressed unto volume V2. Then the work done is given by
W = -P (V2 – V1)
W = -P V , V = V2 – V1 or Vfinal - Vinitial, P = External pressure
If expansion occurs then V2 – V1 will be positive and hence work done will be negative that is
work is done by the system during expansion and if compression occurs then V2 – V1 will be
negative and hence work done will be positive that is work done on the system.
W = -Pex V
Negative sign is given for the expression of correct sign convention of work done.
Work done in isothermal reversible expansion of ideal gas
W = -2.303 nRT log

Or W = -2.303 nRT log

n = Moles of gas

43
 R = Gas constant = 8.314 Joule mol-1 K-1 = 2.0 cal mol-1 K-1
Internal Energy or Intrinsic Energy
The total energy possessed by a substance in a particular state is called its internal energy. Its
numerical value is equal to the summation of energies of various forms contained by the atoms
and molecules of the system e.g. U = Un + Ue + Ub + Ut+ Ur + Uv
Where Un is nuclear energy, Ue is electronic energy, Ub is bond energy, Ut, Ur and Uv are
translational, rotational and vibrational kinetic energies.
As obvious, absolute value of internal energy for a particular system cannot be determined.
More significant term is change in the internal energy ( E) or ( U)
U = U2 – U1 or U = Up – Ur
Where, Up = internal energy of product
Ur = internal energy of reactant
First law of Thermodynamics:
This law states that Energy can neither be created nor be destroyed although it may be
transferred from one substance to the other and may be converted from one form to the other.
mathematically” U=q+W
Where q is amount of heat absorbed while W is work done on the system.
Enthalpy: It is defined as the total energy associated with any system which includes its internal
energy and also energy due to its pressure and its volume.
It is mathematically represented as H = U+ PV
It is also called heat content of the system.Change of enthalpy can be determined. H = H2 – H1
or H = Hp – Hr. Change of enthalpy is a state function and does not depend on the path
adopted. It is defined as the amount of heat evolved or absorbed at constant pressure.
H = qp

Relation between Internal Energy Change ( U) and Enthalpy Change H)

H = (U2 + PV2) – (U1 + PV1)

= (U2 – U1) + P (V2 – V1)

H= U+P V

Further PV = nRT and

P V = ng RT so put the value in equation

H = U + ngRT where n is the change in number of moles of gaseous reactants and

gaseous products H and U will be equal when number of moles of gaseous products and
gaseous reactants are equal.

Heat capacity (C)

It is defined as amount of heat required to raise the temperature by one degree Celsius or one
Kelvin of given substance. If heat capacity is determined at constant volume then represented
by Cv and at constant pressure by Cp.

C=
44
 Cp = p

Cv = v Where, q = amount of heat

H = heat exchange at constant pressure

U = heat exchange at constant volume

For liquid and solid the value of Cv and Cp is approximately same but for gases value of Cv and
Cp are different.

Molar heat capacities: The heat capacity of one mole of gas is called as molar heat capacity.
Relationship between Cp and Cv for a given gas Cp is greater than Cv because at constant
pressure expansion of gas takes which require heat and the difference between Cp and Cv for
one mole of gas is as under

Cp – Cv = R For one mole of gas

Ratio of molar heat capacity: It is represented by and gives idea about atomicity of gas.
=

Value of Cp Value of Cv = Atomicity

1.66 Monoatomic

1.40 Diatomic

4R 3R 1.33 Triatomic

Specific heat capacity (S):

Amount of heat required to raise the temperature of one unit mass (1g) by one degree Celsius
or one Kelvin is called as specific heat capacity.

S=

Or q=mS

Specific heat capacity molecular mass = molar heat capacity

Measurement of Internal Energy Change ( U) and Enthalpy Change H):

U is the change in internal energy at constant volume. Since at constant volume V = 0

and therefore work done is zero. It is determined by using bomb calorimeter. In which sample of
compound is burnt in presence of pure oxygen and change in temperature of water is noted
45
which gives U. In bomb calorimeter sample of compound and oxygen acts as system where as
water and bomb represents surrounding. The H is enthalpy change at constant pressure and
determined by calorimeter. In which reaction is carried out in a foamed polystyrene cup. The
enthalpy change is determined by difference in initial and final temperature.

U = qv = Cv T

H = qp = Cp T

Where,Cv = heat capacity of bomb calorie meter and its content at constant
volume.

Cp = heat capacity of calorie meter and its content at constant pressure

U = Up - Ur

For exothermic reaction U or H is negative. For endothermic reaction U or H is positive

Thermo chemical equation:A balanced chemical equation with involved enthalpy change is
called as thermo chemical equation. For example

N2 (g) + 3H2(g) 2NH3(g) + 92 kJ

H reaction = - 92 kJ

Exothermic reactions: These are the reactions in which heat is evolved. In such reactions HP <
HR, hence H is negative.

Endothermic reactions: These are the reactions in which heat is absorbed. In such reactions
HP> HR, hence H is positive.

Enthalpy of reaction: It is the amount of heat evolved or absorbed at constant temperature and
under constant pressure when numbers of moles of reactants as represented by the chemical
equations have completely reacted.

Standard state is defined as state of a substance in pure form at one bar pressure and 298 K.

Enthalpy of formation: It is the amount of heat evolved or absorbed when 1 mole of compound
is formed from its constituent elements under given condition of temperature and pressure.

When the substances involved are in standard state it is called standard enthalpy of formation.

C (s) + O2 (g) CO2 (g) Hf0 = - 393.5 kJ

Standard enthalpies of formation of elements are arbitrarily fixed as zero. Standard enthalpy of
formation ( Hf 0) can be used to calculate the standard enthalpy of reaction ( H0) as:

H0 = Hf0 (Products) - H f0 (reactants)

Enthalpy of combustion: It is defined as the amount of heat evolved when one mole of a
compound is burnt (completely oxidized) in excess air or oxygen.

46
 CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H = - 890.4 kJ

Combustion is always exothermic and so enthalpy of combustion may be used in rating the
quality of fuel.

Calorific value of food or fuel: It is defined as the amount of heat produced when one gram of
food or fuel is completely burnt in excess of air or oxygen e.g. Calorific value of milk is 3.2 while
that of ghee is 37.6. In case of fuels. Its value for hydrogen is 150 kJ while for wood it is only 17
kJ.

Enthalpy of Solution: It is defined as the heat change accompanying the dissolution of one
mole of a substance in such a large excess of solvent so that further dilution does not produce
any heat change. It is also called differential enthalpy of solution and the change in enthalpy
during dissolution of one mole of a substance in certain amount of solvent to prepare solution of
given concentration is called integral enthalpy of solution.

NH4Cl (s) +aqua NH4+ (aq) + Cl- (aq)

H = + 15 kJ

Enthalpy of hydration: It is the heat change accompanying the hydration of one mole of
anhydrous salt to a specific hydrated state.

CuSO4 (s) + 5 H2O (l) Cu SO4 .5 H2O (s)

H = - 78.2 kJ

Enthalpy of neutralisation: It is the enthalpy change accompanying the complete

neutralisation of one gram-equivalent of an acid by a base or vice versa in dilute solutions.

KOH (aq) + HNO3 (aq) KNO3 (aq) + H2O (l)

H = - 57.1 kJ

Its value for a strong acid against a strong base or vice versa remains constant.

Enthalpy of fusion: It is defined as the enthalpy change the accompanying the conversion of
one mole of a solid substance into its liquid state at its melting point.

H2O (s) H2O (l) H = + 6 kJ

Enthalpy of vaporization: It is defined as the amount of heat required to convert one mole of
liquid into its vapour phase at its boiling point.

H2O (l) H2O (g) H = + 40.6 kJ

Enthalpy of sublimation: It is amount of heat required to convert one mole of a solid directly
into its vapour phase at a temperature below its melting point.

I2 (s) l2 (g) H = + 62.4 kJ

47
Bond Energy:

The enthalpy change during the breaking of covalent bonds present in one mole of
gaseous substance is called as bond enthalpy. For diatomic molecules it is also called as
dissociation enthalpy. The bond energy of identical bonds present in a molecule are not same
and depend upon environment of molecule.

Example H – O – H H + OH – x kJ

O–H O + H –y kJ

Here x < y yet both are identical H – O bonds.

Due to above fact for a polyatomic molecule average bond enthalpy is considered
o
rH = Ho bond of reactants - Hobond of products

Example N2 + O2 2NO

o
rH = [ Ho bond of N2 + Hobond of O2 ] – [ 2 Hobond of NO ]

Hess’s law of constant heat summation: The enthalpy change accompanying a chemical or
physical process is same whether it involves one path or the other through one step or several
steps.

PATH-I
A (∆H) B

( ∆H1) ( ∆H4)

C E
PATH-II
D
( ∆H2) ( ∆H3)
Enthalpy change in path l is H while that of path ll is the sum of H1, H2, H3 and H4
therefore, H = H1 + H2 + H3 + H4

Hess’s law is a consequence of first law of thermodynamics. If it not so, a little heat may either
be destroyed or be created which is not possible.

Applications of Hess’s Law:

1. Calculate the enthalpy of formation of substances which cannot be measured directly and
experimentally.

2. With its help enthalpy of formation of allotropic modifications can be determined.

3. Similarly enthalpy of hydration, combustion etc. can also be calculated.

Spontaneous processes:

48
 In the forward and backward direction of a process energy remains conserved but the
processes occurs in one direction spontaneously and in opposite direction with the help of
external agency for example the cooling of tea at room temperature occurs spontaneously but
its heating does not in the same way mixing of gases formation of ink solution are spontaneous
but its reverse does not.

All spontaneous processes occur till equilibrium is reached. At equilibrium process proceeds in
both directions with same rate hence net change does not observed.

The processes are spontaneous in such a direction where decrease in potential energy is found.
There is only one spontaneous process which occurs without change in energy, is expansion of
ideal gases into vacuum in insulated containers i.e., q = 0 and w = 0 hence U = 0.

Entropy:

It is thermodynamic property which measures randomness or disorder of a system. The

more disorder or randomness, the higher will be entropy, e.g. solid < liquid < gas.

Entropy of a system is state function, i.e. it depends upon initial and final state of the system.
When the state of a system changes, the entropy also changes.It is denoted by S.

Change in entropy S = Sfinal - Sinitial

S= =

Where q is heat supplied isothermally and T is absolute temperature.

• For a irreversible spontaneous process S = +ve

• For a reversible change at equilibrium S = 0
• Entropy increases with increase in temperature, decreases with decrease in
temperature.

The unit of entropy is Joules per Kelvin (JK-1).

Entropy of fusion ( Sfus):The change in entropy when one mole of a solid substance changes
into its liquid state at its melting temperature is known as entropy of fusion. Thus,

Sfus = Sliquid – Ssolid= or Sfus =

Where Sfus = entropy of fusion, Sliquid= molar entropy of liquid, Ssolid = molar entropy of the
solid Hfus = molar enthalpy of fusion, Tm = melting temperature (in Kelvin) of the solid

Entropy of vaporization ( Svap): The change in entropy when one mole of liquid changes into
its vapours at its boiling temperature, is known as entropy of vaporization. Thus

Svap = Svap–Sliq = or Svap =

Where Svap = entropy of vaporization, Sliq = molar entropy of the liquid, Svap = molar entropy
of vapour Hvap = molar entropy of vaporization Tb = boiling temperature (in Kelvin) of the liquid.

49
Criteria of spontaneity in terms of entropy change:

Thus, the total entropy change ( Stotal) will be equal to the sum of the change in entropy
of the system ( Ssystem) and the change in entropy of the surroundings ( Ssurroundings), i.e.,

Stotal = Ssystem+ Ssurroundings

For a spontaneous process, Stotal must be positive i.e. Stotal = Ssystem + Ssurroundings > 0

Similarly, we can say that if Stotal is negative, the process will be non spontaneous and if Stotal
is equal to zero, the process will be in equilibrium.

Gibbs energy:

In order to understand the true criterian for a process to be spontaneous, a new function
called free energy is introduced. It is also known as Gibb’s free energy and is denoted by the
symbol ‘G’. Mathematically, it is defined as G = H – TS

Where, H is the enthalpy T is the absolute temperature and S is the entropy of the system. For
an isothermal process, let G1, H1 and S1 be the free energy, enthalpy and entropy of the system
is in the initial state and G2, H2and S2 be the corresponding values in the final state.

G1 = H1 – TS1 (initial state) G2 = H2 – TS2 (final state)

G2 – G1 = (H2 – H1) – T(S2- S1)

G= H-T S

Where G, H and S are the changes in Gibb’s free energy, enthalpy and entropy of
the system. The above equation is known as Gibb’s Helmholtz equation.

If in a process H be the enthalpy increase and G be the free energy increase, the
efficiency of the process for doing useful work would be G/ H, or

Efficiency = =

Gibbs energy change and Spontaneity:

We have already discussed that

Stotal = Ssystem + Ssurroundings …(i)

If a process is carried out at constant temperature and pressure and qp is the heat lost by the
surroundings, then

Ssurroundings = …(ii)

But, at constant pressure, qp = H

Therefore, equation (ii) becomes Ssurroundings =

50
Substituting the value in (i) we get

Stotal = Ssystem- or T Stotal = T Ssystem - H …(iii)

But at constant temperature and pressure

G = H – T Ssystem So T Ssystem = H - G

Putting the value in (iii) we get

T Stotal = H - G - H = - G

or G = - T Stotal …(iv)

i. If Stotal is positive, the process is spontaneous

ii. If Stotal is zero, the process is in equilibrium
iii. If Stotal is negative, the process is non- spontaneous.

On applying these conclusions to equation (iv), it can be concluded that

i. If G is negative, the process will be spontaneous

ii. If G is zero, the process will be in equilibrium
iii. If G is positive, the process is not spontaneous.

Thermodynamic criterion for the feasibility of a process:

We know that spontaneity of a process neither depends only upon enthalpy factor ( H) nor on
randomness factor ( S). But it is the resultant ( G) of both the factors which is responsible for
spontaneity of a process. The two factors H and S are related to each other as

G= H-T S

Only those processes for which free energy change ( G) is negative can occur spontaneously.
The Gibb’s Helmohltz equation, G = H - T S, helps in drawing the following conclusions:

A. When H and T S are both negative, i.e., the energy factor favours the process
and the randomness factor opposes it.

Then,

i. If H > T S; G is negative, hence, the process is spontaneous.

ii. If H < T S; G is positive, hence, the process is non-spontaneous.
iii. If H = T S; G is zero, hence, the process is equilibrium.
B. When H and T S are both positive, i.e., the energy factor opposes the process
and the randomness factor favours it.
Then,

i. If H> T S; G is positive, hence, the process is non-spontaneous.

ii. If H < T S; G is negative, hence, the process is spontaneous.

51
 iii. If H = T S; G is zero, hence, the process is in equilibrium.

C. When H is positive and T S negative, i.e. the energy factor and the
randomness factor, both oppose the process. G will be highly positive, hence,
the process will be highly non spontaneous.
D. When H is negative and T S is positive. i.e., the energy factor and randomness
factor, both favour the process. G will be highly negative, hence, the process
will be highly spontaneous.

Second law of thermodynamics:

The entropy of universe is continuously increasing and tends to a maximum due to spontaneous
process taking place in it

Ssystem + Ssurrounding> 0,i.e. Stotal > 0

Third law of thermodynamics:

The entropy of any pure crystalline substance approaches zero as temperature

approaches absolute zero.

Standard Gibbs energy change ( Go) and equilibrium constant (K):

The standard free energy change is defined as the free energy change for a process at
298 K in which the reactants in their standard states. It is denoted by the symbol Go

The standard free energy of formation ( Go f ) of a compound is defined as the change in free
energy when one mole of a compound is formed from its constituent elements in their standard
state. The standard free energy of formation of an element in its standard state is zero.

Thus, Go = Gfo (products) – Gfo (reactants)

Relation between standard Gibbs energy and equilibrium constant

Go = -RT ln K

Go= - 2.303 RT log K

Effect of temperature on Spontaneity of reaction

0 0 0
Description
- + - Reaction spontaneous at all temperature
- - ( at low T ) Reaction spontaneous at low temperature
- - + ( at high T ) Reaction nonspontaneous at high temperature
+ + + (at low ) Reactionnon spontaneous at low temperature
+ _ (at high T ) Reaction spontaneous at high temperature
+ _ + (at all T ) Reaction nonspontaneous at all temperature

52
 UNIT 7 : EQUILIBRIUM

Introduction:
In this unit we will be able to explain equilibrium in physical state, explain equilibrium in
dissolution of solid or gases in liquids, explain chemical equilibrium, state law of equilibrium,
explain homogeneous & heterogeneous equilibria, write the expression for equilibrium in both
the above equilibria, explain characteristics of the equilibrium constant, discuss the applications
of equilibrium constant, state Le Chatelier’s principle, discuss factors affecting the equilibria,
explain ionic equilibrium in solution, discuss concept of acids & bases in terms of Arrhenius,
Bronsted –Lowry &Lewis theory, explain pH scale & classify acids & bases as strong & weak,
explain factors affecting acid strength, explain the hydrolysis of salts & calculate pH of their
solutions, define buffer solution & explain importance of buffer solutions in daily life, define the
solubility product, use Ksp to calculate solubility of a salt in water & predict whether precipitation
will occur or not.

• Predicting the conditions required for maximum yield of chemicals during their industrial
manufacture.
• Common ion effect & solubility product in qualitative analysis of salts.
• Physical equilibrium of water & steam is used in steam cooking.
• Physical equilibrium between dissolved gas & its partial pressure is used for making
aerated drinks.
• pH & Buffer solutions are important in biological processes & the pharmaceutical
industries.
• The common ion effect is also used for almost complete precipitation of a particular ion
as its sparingly soluble salt with very low value of Ksp for gravimetric determination
• Pure NaCl is obtained by passing HCl gas through it. Due to common ion NaCl is
precipitated.
• pH of solutions is important for quality of soil, intake of medicines, to study pollution in
water bodies etc.

Important Points of the unit:

Reversible reaction: A reaction that can take place in forward as well as backward direction.

Irreversible reaction: A chemical reaction that cannot take place in the backward direction.

Equilibrium State: A state of the system when its observable properties do not change at a
given set of conditions. At this stage rate of the forward as well as reverse reactions are equal.
Equilibrium can be established in both physical & chemical processes.

53
 Concentration vs time graph Rate vs time

graph

Equilibrium in physical processes: e.g: Phase transformations (solid- liquid, liquid – vapour,
solid – gas)

Process Conclusion
Liquid vapour is constant at given T
H2O(l) H2O(g)
Solid liquid M.pt. is fixed at constant pressure
H2O(s) H2O(l)
Solute(s) solute(solution) Concentration of solute in solution is
Sugar(s) sugar (solution) constant at a given temperature.
Gas(g) Gas (aq) [gas(aq)]/[gas(g)] is constant at a given
CO2(g) CO2 (aq) temperature
[CO2(aq)]/[CO2(g)] is constant at a given
temperature

Henry’s law for dissolution of gases in liquids:

The mass of a gas dissolved in a given mass of a solvent at any temperature is

proportional to the pressure of the gas above the solvent.

General Characteristics of Equilibria involving Physical Processes:

• The equilibrium is attained only in a closed / isolated system.

• All measurable properties attain a constant value.
• The equilibria are all dynamic ones. Two opposing processes take place simultaneously at
equal rates.
• The magnitude of measurable quantities at any stage indicates the extent to which the
physical process has proceeded before reaching equilibrium.

Equilibrium in Chemical Processes:

Dynamic Equilibrium: State of a reversible chemical reaction where the forward reaction rate
is equal to the reverse reaction rate, resulting in no net change in composition.

Homogeneous Equilibrium: Equilibrium in which the reactants & products are in the same
phase. For eg: N2(g) + 3H2(g) 2NH3(g)

CH3COOC2H5(aq) + H2O(l) CH3COOH(aq) + C2H5OH(aq)

54
Heterogeneous Equilibrium: Equilibrium in which the reactants and products have different
phases. For eg: CaCO3(s) CaO(s) + CO2(g)

CO2(g) + C(s) 2CO(g)

Law of Equilibrium: At a given temperature the product of the concentrations of the reaction
products raised to the respective stoichiometric coefficients in the balanced chemical equations
divided by the product of concentrations of the reactants raised to their individual stoichiometric
coefficients has a constant value.

Equilibrium Constant Kc: For the reaction: at equilibrium

Equilibrium constant has a constant value at a fixed temperature & at this stage all the
macroscopic properties such as concentration, pressure etc become constant.

For a gaseous reaction equilibrium constant can be expressed as Kp which is written by

replacing all concentration terms in Kc by the partial pressures

In using the above expressions, the concentrations or partial pressure of solids & liquids are
taken to be UNITY.

Relation between equilibrium constants for a general reaction & its multiples:

Chemical equation Equilibrium constant

: Kc
: Kc’ = 1/ Kc
:n Kc’’ = (Kc)n

55
Applications of Equilibrium constant

a. To predict the extent of a reaction on the basis of its magnitude.

If Kc> 103, products predominate over reactants, the reaction proceeds nearly to completion.

If Kc< 10-3, reactants predominate over products, the reaction proceeds rarely.

If 10-3< Kc< 103, appreciable concentrations of both reactant and products are present.

b. To predict the direction of the reaction.

Reaction Quotient (Q). The ratio of product of molar concentrations of the products to
the product of molar concentrations of reactants with each concentration term raised to the
power equal to the stoichiometric co-efficient of that species is called reaction quotient.

At equilibrium, Qc = Kc.

At concentrations other than equilibrium, Qc ≠ Kc

If Qc > Kc, the reaction will proceed in the direction of reactants (reverse reaction).

If Qc < Kc, the reaction will proceed in the direction of products (forward reaction).

If Qc = Kc, the reaction mixture is already at equilibrium.

Thermodynamic Principle of equilibrium:

At equilibrium ΔG = 0, so,

If ΔG is negative the reaction is spontaneous & proceeds in forward direction.

If ΔG is positive the reaction is nonspontaneous & proceeds in reverse direction

If ΔG is zero the reaction has achieved equilibrium.

Le Chatelier’s principle: This principle states that the change in any factor such as
temperature, pressure, concentration, etc will cause the equilibrium to shift in such a direction
so as to reduce or counteract the effect of the change.

It can be used to study the effect of various factors such as temperature, concentration,
pressure, catalyst and addition of inert gases on the direction of equilibrium and to control the
yield of products by controlling these factors.

Catalyst does not affect the equilibrium composition of a reaction mixture but increases
the rate of chemical reaction by providing a new lower energy pathway for the conversion of
reactant to products and vice-versa.

56
Factors affecting a system at equilibrium:

Factor Direction of reaction when Kc value

increased Decreased
Conc. Of reactants Forward( →) Backward() Remains same
Conc. Of Products Backward() Forward( →) Remains same
Pressure Towards lesser no Towards greater no Remains same
of moles of gas of moles of gas
Temperature In the direction in In the direction in Changes
which it is which it is exothermic
endothermic
Addition of Inert No change Remains same
Gas
at constant volume
Catalyst Increases rate of attaining equilibrium. No Remains same
change in the equilibrium

Equilibria involving ions:

Substances that conduct electricity in aqueous solutions are called electrolytes. Acids,
bases and salts are electrolytes and the conduction of electricity by their aqueous solutions is
due to anions and cations produced by the dissociation or ionisation of the electrolytes in
aqueous solution. The strong electrolytes are completely dissociated in aqueous solution
while in the weak electrolytes there is equilibrium between ions and unionised electrolyte
molecules. The fraction of the number of the molecules of weak electrolyte that ionizes is known
as degree of ionization.

According to Arrhenius, acids give hydrogen ions while bases produce hydroxyl ions in their
aqueous solutions.

Brönsted-Lowry on the other hand, defined an acid as proton donor and bases as proton
acceptor.

When Brönsted-Lowry acid reacts with a base, it produces its conjugate base and
conjugate acid corresponding to the base with which it reacts. Thus the pair of acids & bases
which are formed from each other by the gain or loss of a proton are called conjugate acid –
base pairs.

57
 Acid = Conjugate base + H+

Base + H+ = Conjugate acid

Lewis defined an acid as an electron pair acceptor and a base as electron pair donor.

Concept ACIDS BASES Examples

Arrhenius + – HCl & NaOH
Give H ions in solution Give OH ions in solution
Bronsted- Lowry + + HCl & NH3
H ion/ proton donors H ion/ proton acceptors
Lewis Electron pair acceptors Electron pair donors BF3 & NH3
Ionisation constants: The expressions for ionization equilibrium constants of weak acids
(Ka) and weak bases (Kb) are

Strength of acids or bases are measured in terms of their respective dissociation

constants Ka (or pKa = -logKa) and Kb (or pKb = -logKb).
Larger value of Ka or lower value of pKa corresponds to greater strength of acid.

Similarly larger value of Kb or lower value pKb corresponds to stronger base.

Ionic Product constant of water(Kw): the ionic product [H+][OH-] = 1×10-14 at 25oC. It
increases with increase in temperature and decreases with decrease in temperature.

pH of solution is –log[H3O+]

pOH of solution is –log[OH--]

For any solution at 25oC

pKw = pH + pOH= 14

The common ion effect: is the shift in an ionic equilibrium caused by the addition of a solute
that provides an ion that takes part in the equilibrium.

The addition of common ion reduces the degree of dissociation of a weak acid or weak base.

58
Hydrolysis of salts: involves the interaction of the ions of the salt with water molecules in
solution to give acidic or basic solution.

For a Salt of weak acid & strong base: pH = ½(pKa + pKw + logC)

For a Salt of strong acid & weak base: pH = ½(pKw – logC - pKb)

For a Salt of weak acid & weak base: pH = ½(pKw + pKa - pKb)

Buffer Solution: It is a solution which resists the change in its pH value on the addition of small
amount of acid or base.

A buffer solution is generally a mixture of weak acid and salt of its conjugate base (for
eg: CH3COOH & CH3COONa) or weak base and salt of its conjugate acid (For eg: NH4OH &
NH4Cl).

pH of buffer solution is given by Henderson-Hasselbalch equation:

For acidic buffers For basic buffers

Solubility Product (Ksp): It is a product of concentration of ions of electrolyte at the saturation

point with each concentration term raised to the power equal to numerical coefficient of that
species in the balanced equation. It is the highest value of ionic product for a sparingly soluble
salt. For a general salt

For example: For Ag2SO4 the equilibrium is Ag2SO4(s) 2Ag+ + SO 42--

Ksp for Ag2SO4 can be written as

Applications of solubility product:

i) To calculate the solubility of a sparingly soluble salt.

If S is the solubility in mol/L of AxBy, then Ksp =( xS)x.( yS)y

Ksp = xxyyS(x+y)

If S is the solubility in mol/L of Ag2SO4, then Ksp = 22S3

ii) To predict whether precipitation will occur or not when two solutions are mixed in a double
displacement reaction. If Qsp > Ksp then precipitation will occur.
iii) The solubility of a sparingly soluble salt further decreases due to common ion effect.

59
 UNIT 8: REDOX REACTIONS
Introduction:

Redox reactions form an important class of reactions in which oxidation & reduction
occur simultaneously. Transformation of matter occurs through various types of reactions. We
observe rusting of iron, fading of colour from clothes. Redox reactions are one such reaction
through which a number of physical & biological phenomena take place. Burning of fuels,
Electrochemical processes for extraction of highly reactive metals & non metals, manufacturing
of many chemical compounds like caustic soda, operation of dry & wet batteries & corrosion of
metals fall within the purview of redox processes. Environmental issues like hydrogen economy
& development of ozone hole are also redox phenomena.

Definitions of redox reactions:

OXIDATION REDUCTION EXAMPLES

Gain of oxygen Loss of oxygen

Loss of Gain of
hydrogen hydrogen

Gain of Loss of
electronegative electronegative
element element
Loss of Gain of
electropositive electropositive
element element

Loss of Gain of
electrons electrons

Oxidant or oxidizing agent: a substance that takes electron from another substance. The
oxidant gets reduced during the reaction.

Reductant or reducing agent: a substance that gives electron to another substance. The
reductant gets oxidised during the reaction.

Oxidation Number : The residual charge of an atom, when all the atoms from the molecule are
assumed to be removed as ions by counting the shared electrons with the more electronegative
atom.

Mnemonics to remember:

LEO (Loss of electrons – oxidation)

GER (Gain of electrons – reduction)

60
 Rules for assigning oxidation number to an atom:

i. The oxidation number of the element in the free or elementary state is always zero.
ii. The oxidation number of the element in monoatomic ion is equal to the charge on the ion.
iii. The oxidation number of fluorine is always –1 in all its compounds.
iv. The oxidation number of other halogens is also –1 in most compounds except with Fluorine &
Oxygen.
v. The oxidation number of hydrogen is +1 in most compounds except in metal hydrides in
which it is –1.
vi. The oxidation number of oxygen is –2 in most compounds, however in peroxides (containing
–O—O--) it is –1 & with Fluorine it shows +ve oxidation no:
vii. The algebraic sum of the oxidation number of all the atoms is equal to the charge of the
species.

In terms of oxidation no: oxidation is the increase in +ve oxidation number or decrease in –ve
oxidation number, & reduction is the increase in --ve oxidation number or decrease in +ve
oxidation number.

Example 1: H2S + Br2 → 2HBr + S

Oxidation number: +1,-2 0 +1 -1 0

• The oxidation number of S is increasing from -2 to 0. So, H2S is oxidised to S

• The oxidation number of Br2 Is decreasing from 0 to -1. So Br2 is reduced to HBr.

Example 2:

Types of redox reactions:

i. Combination reactions C + O2 → CO2, 3Mg + N2 → Mg3N2,2CO + O2 → 2CO2

ii. Decomposition reactions: 2KClO3 → 2KCl + 3O2 2H2O → 2H2 + O2
iii. Displacement reactions:
a) Metal displacing metal: Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
b) Non-Metal displacing non- metal: Cl2(g) + 2KI(aq) → 2KCl(aq) + I2(s)
c) Metal displacing non-metal: Mg + 2HCl → MgCl2 + H2

61
 iv. Disproportionation reactions: In these reactions an element in one oxidation no: is
simultaneously oxidized & reduced.
P4 + 3OH- + 3H2O→PH3 + 3H3PO2

Cl2 + 2OH- → ClO- + Cl- + H2O

Balancing of redox reactions:

1. by half reaction method:

a) Indicate ON of each atom involved in the reaction on both the reactants as well as product
side. Identify the elements undergoing oxidation & reduction.
b) Divide the skeletal redox equation to two half reaxns – the oxidation half reaction (OHR) &
the reduction half reaction (RHR). Balance the atom that is undergoing oxidation or
reduction.
c) Add electrons to whichever side is necessary to make up for the difference in oxidation no:
For OHR the electrons are added to the product side & for RHR to the reactant side.
d) Balance the charge by addition of H+ (if medium is acidic) or OH—(if medium is basic).
e) Balance the H & O atoms by addition of H2O.
f) Equalise the no: of electrons in the OHR & RHR by multiplying them with suitable integers &
then add the two half reactions to get the overall balanced equation.

2. By oxidation no: method:

a) Indicate ON of each atom involved in the reaction on both the reactants as well as product
side. Identify the elements undergoing oxidation & reduction.
b) Balance the atom that is undergoing oxidation or reduction.
c) Determine the increase or decrease of ON per atom & multiply by no: of atoms undergoing
the change.
d) Equalise the above by multiplying the respective formulae with a suitable integer.
e) Balance charge by addition of H+ (if medium is acidic) or OH—(if medium is basic).
f) Balance H & O by addition of H2O.

Applications of redox reactions:

1. Redox reactions as a basis for titration:

a) One of the titrants which has an intense colour or shows a drastic colour change during the
reaction is used as a self indicator. For eg: MnO4—acts as a self indicator due to the above
properties.
b) In cases where there is no auto colour change, then indicators are used which are oxidised
immediately after the last bit of reactant has been oxidized. For eg: in titrations involving
dichromate ion Cr2O72—which is not a self indicator but oxidises indicators like diphenylamine
just after equivalence point to produce an intense blue colour, thus signalling the end point.
c) Reactions involving I2 can be tracked by adding starch indicator which gives a blue black
colour with I2. So appearance & disappearance of iodine can be identified very sharply.
2) Redox reactions to produce electricity: Galvanic cell: In a Galvanic cell electricity is
produced by a spontaneous redox reaction. Oxidation & reduction take place separately at
the anode & cathode respectively. The electrochemical cell or Galvanic cell is the device in
which chemical energy is converted to electrical energy. This consists of two redox couples

62
UNIT 12: ORGANIC CHEMISTRY- SOME BASIC PRINCIPLES
AND TECHNIQUES

1. Introduction:
Science of organic chemistry is about two hundred years old. Around the year 1780,
chemists began to distinguish between organic compounds obtained from plants and animals
and inorganic compounds prepared from mineral sources. Berzilius, a Swedish chemist
proposed that a ‘vital force’ was responsible for the formation of organic compounds. However,
this notion was rejected in 1828 when F. Wohler synthesised an organic compound, urea from
an inorganic compound, ammonium cyanate.

Chemistry behind the existence of large number of Carbon compounds due to its
tetravalency and catenation.

The shapes of carbon compounds:

According to Hybridization theory, Carbon shows all three types – sp3, sp2 and sp.
sp3 hybridization – tetrahedral shape eg. for Alkanes
sp2 hybridization – trigonal plannar shape for eg. Alkenes
sp hybridization – linear shape for eg. Alkynes

Concept mapping:

Classification of Organic Compounds

Acyclic or open chain Cyclic or closed chain

(eg.CH3-CH3) (eg. cyclopropane)

Alicyclic() Aromatic

Homocyclic Heterocyclic Benzenoid Non–Benzenoid

(Benzene) (Tropolone)

Structural Representations of organic compounds.

1. Complete structural formula

2. Condensed structural formula ethane - CH3CH3, propane - CH3CH2CH3,

butane - CH3CH2CH2CH3

85
3. Bond line representation

butane:
3-methyl pentane:

4. Three-Dimensional Representation
(Wedge Representation)

RULES for IUPAC Nomenclature of organic compounds

(1) First of all the longest carbon chain in the molecule is identified.
(2) The numbering is done in such a way that the branched carbon atoms get the lowest
possible numbers.
(3) If two or more identical substituent groups are present then the numbers are separated by
commas. Lower number is given to the one coming first in the alphabetical listing.
(4) 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.

86
Nomenclature of substituted benzene compounds.

9. Isomerism:
The phenomenon of existence of two or more compounds possessing the same molecular
formula but different properties is known as isomerism. Such compounds are called as isomers.
The following flow chart shows different types of isomerism.

Chain isomerism: Two or more CH3-CH2-CH2-CH2-CH3

compounds differ in carbon Pentane
skeletons CH3-CH-CH2-CH3
І
CH3
2-methylbutane
Position isomerism: Two are more CH3-CH2-CH2-OH CH3-CH-CH3
compounds differ in the position of Propan-1-ol І
substituent or functional group. OH
Propan-2-ol
Functional group isomerism
Stuctural Same molecular formula but differ in CH3-C-CH3 CH3-CH2 -C=O
Isomerism functional group ‫װ‬ І
O H
Propanone Propanal
Metamerism: Arises due to different (1) CH 3 -O-CH2 CH2 CH3

alkyl chains or either side of the Methoxypropane

fuctional group in the molecules CH3-CH2-O-CH2CH3
Ethoxyethane
(2) CH3-CH2-CH2-NH-CH3
N-methylpropanamine
CH3-CH2-NH-CH2-CH3
N-ethylethanamine
Stereoisomerism: same molecular Geometrical isomerism cis butene, trans butene
formula, same structural formula but
different orientation in space

Compound should be mirror image of Optical isomerism Left hand & right hand
each other but should not be super
impose over each other

87
10. Fundamental concepts in organic reaction mechanism

(a) Fission of a Covalent Bond

A covalent bond can get cleaved either by: (i) Heterolytic cleavage, or by (ii) Homolytic
cleavage.
(i) Heterolytic cleavage:
In heterolytic cleavage, the bond breaks in such a manner that the shared pair of electrons
remains with one of the parts.

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.
(ii) Homolytic cleavage:
In homolysis or homolytic cleavage, 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. There are three types of free radicals –
primary (10), secondary (20) and tertiary (30). Their stability increases in the order 10 < 20 < 30.

(b) Nucleophiles and Electrophiles

Nucleophiles are electron rich species and attack at electron deficient centre. (The
word nucleophile means nucleus seeking).
Example for nucleophiles are OH─, CN─, NO2─ , Cl─, Br ─, I─, H2O, NH3, R-NH2 etc.

88
 Electrophiles are electron deficient species attack at electron rich centre. (The word
electrophile means electron seeking).
Example for electrophiles are carbocations (R+), -CHO, >CO etc.

(c) Electron movement in organic reaction

The movement of electrons in organic reactions can be shown by curved-arrow notation. It
shows how changes in bonding occur due to electronic redistribution during the reaction. To
show the change in position
of a pair of electrons, curved arrow starts from the point from where an electron pair is shifted
and it ends at a location to which the pair of electron may move. Presentation of shifting of
electron pair is given below:

Effects in covalent Bonds

Electron Types of effect examples
displacemen
t effects
– I effect 1-chlorobutane
(electron withdrawing CH3 – CH2 – CH2 – CH2 –Cl
effect of groups
attached to alkyl chain)
Inductive EWG :
Effect –X (F, Cl, Br, I), nitro (-NO2), Cyano (CN-), Carboxy (-
(permanent COOH), ester (-COOR), aryloxy (-OAr) etc.
effect)
+ I effect EDG:
(electron donating methyl (-CH3), ethyl (-CH2-CH3) etc.
effect of groups
attached to alkyl chain)
+ R effect
(the transfer of – Halogen, –OH, –OR, –OCOR, –NH2,
electrons is away from –NHR, –NR2, –NHCOR,
an to atom or
substituent group
Resonance attached to the
effect conjugated system)
(permanent - R effect
effect) (when the transfer of – COOH, –CHO, >C=O, – CN, –NO2
electrons is toward an
atom or substituent
group attached to the
conjugated system)

89
 + E effect
(In this effect the pi electrons of the
multiple bond are transferred to that
Electromeric atom to which the reagent get attached)
effect
(temporary -E effect
effect) (In this effect the pi electrons of the
multiple bond are transferred to that
atom to which the attaching reagent
does not get attached)
The delocalization of sigma electron of
Hyperconjuga C-H bond of an alkyl group directly
tion attached to an atom of unsaturated
(Permanent system or to an atom with an un shared
effect) p-orbital

Methods of purification of organic compounds

Once an organic compound is extracted from a natural source or synthesised in the

laboratory, it is essential to purify. The common techniques used for purification are as follows:

Name of
Principle involved in method Examples
Method
Sublimation is used to separate sublimable Salt + Ammonium chloride ,
Sublimation
compound from non-sublimable impurities. Sand + Camphor
Crystallisation is based on the difference in the Impure NaCl
Crystallisation solubilities of the compound and the impurities Impure Copper Sulphate
in suitable solvent.
To separate volatile liquid from non-volatile Acetone + Water,
Distillation
impurities Aniline + Benzene,
Toluene + Benzene
It is based on the difference in boiling points of Crude Oil,
Fractional
two liquids is not much Air
Distillation

This method is used to purify liquids having Glycerol can be separated

Distillation Under
very high boiling points and those, which from spent-lye in soap
reduced pressure
decompose at or below their boiling points. industry
Differential The immiscible liquids separate out in layers Water + Kerosene,
Extraction depending on their densities. Water + Petrol,
(Separating Water + Organic compound
funnel)
Paper chromatography is partition Separation of colour
Chromatography Chromatography based on continuous component from ink.
( Paper differential partitioning of components of a
Chromatography) mixture between stationary and mobile phase. Drugs from blood

90
Qualitative analysis of organic compounds:

Preparation of Lassaigne’s extract or sodium fusion extract - A small piece of

sodium metal is heated gently in a fusion tube till it melts to a shining globule. At this stage, a
small amount of substance is added and the tube is heated strongly. The red hot tube is
plunged into distilled water contained in a mortar and crushed with pestle. The contents are
boiled for some time, cooled and then filtered. The filtrate is known as Sodium fusion extract or
Lassaigne’s extract.

Test Observation Inference

O.C. + Copper (II) oxide Lime water becomes
Presence of carbon is
Test for and heat it. Evolved CO2 turbid (white ppt. is
confirmed.
Carbon gas passed over lime obtained)
water
Test for O.C. + Copper (II) oxide Colourless copper Presence of Hydrogen
Hydrogen and heat it and gas sulphate crystal changes is confirmed
coming out is passed over into blue
anhydrous copper
sulphate
Test for Sodium fusion extract +
Nitrogen Prussian blue colour is Presence of Nitrogen
Heat it up to boil formed is confirmed.
Presence of Sulphur is
Sodium fusion extract +
Black ppt. is formed confirmed.
Test for Acetic acid + Lead acetate
Sulphur
Sodium fusion extract + Violet coloured solution is Presence of Sulphur is
Sodium nitroprusside formed confirmed.
White ppt. is obtained
Presence of Chlorineis
which is soluble in
detected
NH4OH
Test for Sodium fusion extract + Yellowish ppt. is obtained
Halogen Presence of Bromine
Nitric acid + which is sparingly soluble
is detected.
in NH4OH

Yellowish ppt. which is Presence of Iodine is

insoluble in confirmed

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Quantitative analysis: estimation of elements:
Element Name of Principle Percentage of Element
Method
A known mass of an organic % of C =
Liebig’s compound is burnt in the presence of
Carbon y=mass of co2
method excess oxygen and copper (ii) oxide.
m=mass of o.c
Carbon and hydrogen in the
compound are oxidised to carbon % of H =
Liebig’s
Hydrogen dioxide and water respectively. x=mass of water
method
m=mass of o.c
The nitrogen containing organic
% of N =
compound, when heated with copper
Duma’s m=mass of o.c
oxide in an atmosphere of carbon
Method v = volume of dry nitrogen
dioxide yields free nitrogen in addition
to carbon dioxide and water. at S.T.P
The compound containing nitrogen is
heated with concentrated sulphuric
Nitrogen
acid. Nitrogen in the compound get
converted to ammonium sulphate. % of N =
Kjeldahl’s
The resulting mixture is then heated m=mass of o.c
method
with excess of NaOH. The liberated M= molarity of NaOH
ammonia gas is absorbed in an
excess of standard solution of
sulphuric acid.
A known mass of an organic compound is % of Cl =
heated with fuming nitric acid in the
presence of silver nitrate contained in a
hard glass tube known as Carius Tube, in % of Br =
a furnace. Carbon and hydrogen present
Carius in the compound are oxidised to carbon
Halogen
Method dioxide and water. The halogen present % of I=
forms the corresponding silver halide m=mass of o.c
(AgX).
m1=mass of AgCl,AgBr &
AgI

A known mass of an organic

compound is heated in Carius tube
with sodium peroxide or fuming nitric % of S =
Carius acid. Sulphur present in the m=mass of o.c
Sulphur
Method compound is oxidised to sulphuric m1= mass of barium
acid. It is precipitated as barium sulphate
sulphate by adding excess of barium
chloride solution in water.
A known mass of organic compound
is heated with fuming nitric acid
Phos whereupon phosphorous present in
- % of P =
phorous the compound is oxidised to
Phosphoric acid. It is precipitated as
Ammonium Phosphomolybdate by
92
 adding ammonia and Ammonium
Molybdate
Alternatively, phosphoric acid may be % of P =
precipitated as magnesium
m=mass of o.c
- ammonium phosphate by adding
m1= mass of ammonium
magnesia mixture which on ignition
phosphor molydate
yields magnesium pyrophosphate

A known mass of an organic

compound is decomposed by heating
in a stream of nitrogen gas. The
mixture of gaseous products
%of O =
containing oxygen is passed over red-
Oxygen - hot coke when all the oxygen is m=mass of o.c
converted to carbon monoxide. This m1= mass of CO2
mixture is passed through warm
iodine pentoxide when carbon
monoxide is oxidised to carbon
dioxide producing Iodine.

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 UNIT 13: Hydrocarbons

Introduction:

The compounds of carbon and hydrogen are called hydrocarbons. Hydrocarbons play a
key role in our daily life. ‘LPG’ and ‘CNG’ used as fuels. LPG is liquified petroleum gas whereas
CNG stands for compressed natural gas. ‘LNG’ (liquified natural gas) is also in news these
days. Petrol, diesel and kerosene oil are obtained by the fractional distillation of petroleum found
under the earth’s crust. Coal gas is obtained by the destructive distillation of coal. Natural gas is
found in upper strata during drilling of oil wells. LPG is used as a domestic fuel with the least
pollution. Kerosene oil is also used as a domestic fuel but it causes some pollution. All these
fuels contain mixture of hydrocarbons, which are sources of energy.
Hydrocarbons are also used for the manufacture of polymers like polythene,
polypropene, polystyrene etc. Higher hydrocarbons are used as solvents for paints. They are
also used as the starting materials for manufacture of many dyes and drugs. Thus hydrocarbons
are very important in our daily life.
Aliphatic Hydrocarbons Aromatic Hydrocarbons
➢ Alkanes, Alkenes and Alkynes ➢ General introduction of benzene
➢ Preparation and Nomenclature ➢ Resonance Structure of Benzene
➢ Isomerism and conformations ➢ Orbital structure of benzene
➢ Saw Horse and Newman ➢ Preparation of Benzene
projections
➢ Structure of hydrocarbons ➢ Physical properties of benzene
➢ Physical properties ➢ Chemical reactions of Benzene
➢ Chemical properties ➢ Electrophilic substitution of benzene
➢ Various Name reactions ➢ Mechanism of various chemical reactions
➢ Mechanism of reactions ➢ Directive influence of monosubstituted
arenes
➢ Reaction map of hydrocarbons ➢ Carcinogenicity and toxicology

Classification of Hydrocarbons:
A. Alkanes:
Alkanes are saturated open chain hydrocarbons containing carbon - carbon single
bonds. Methane (CH4) is the first member of this family. These hydrocarbons are inert under
normal conditions as they do not react with acids, bases and other reagents. Hence, they were
earlier known as paraffins (latin : parum, little; affinis, affinity). The general formula for alkanes is
CnH2n+2, where n stands for number of carbon atoms and 2n+2 for number of hydrogen atoms in
the molecule.
All Alkanes have tetrahedral structure and are joined together in which C-C and C-H
bond lengths are 154 pm and 112 pm respectively. First three members of alkane family are
given below.

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 The sigma bond formation and orbital structure of methane is given below

Orbital structure of methane:

➢ IUPAC Nomenclature of alkanes:
1. Identify the longest chain or main chain
2. Give Number on each carbon of longest chain
3. Number the chain consecutively, starting at the end nearest a substituent group or
functional group
4. If two or more side chains are in equivalent positions, assign the lowest number to the
one which will come first in the name. A cyclic (ring) hydrocarbon is designated by the
prefix cyclo- which appears directly in front of the base name.

Isomerism in Alkanes: Alkanes show structural isomerism called chain isomerism.

➢ Conformations of Alkanes:
The different spatial arrangements of atoms arising due to free rotation around a C-C
single bond are called conformations or conformers or rotamers.
For example Conformations of ethane:
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.
These conformations can be represented by Sawhorse and Newman projection
formulas.
a) 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 attached to it corresponding to three
hydrogen atoms. Sawhorse projections of eclipsed and staggered conformations of ethane are
as follows:

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b) 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:

Note: In both the cases staggered conformation has lower energy and hence has high stability
than eclipsed conformation.
B. Alkenes:
Alkenes are unsaturated hydrocarbons containing at least one double bond. They are
also known as olefins (oil forming) since the first member, ethylene or ethene (C2H4) was found
to form 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 isomerisms
shown by alkenes are chain isomerism and position isomerism. The stereo isomerism shown by
alkenes is geometrical isomerism.
(i) Geometrical Isomerism
The isomerism arising due to the difference in the spatial arrangement of atoms around
carbon-carbon double bond is called geometrical isomerism.
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 formula YX C = C XY can show geometrical isomerism as follows:

Note: 1. cis isomer has higher dipole moment due to its higher polarity.
2. trans isomer has higher melting point but cis Isomer has higher boiling point.

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 C. Preparation of Hydrocarbons:
Preparation of Alkanes Preparation of Alkenes Preparation of Alkynes
1. From unsaturated 1. From alkynes: 1. From Calcium Carbide:
hydrocarbons: CaO + 3C → CaC2+ CO
CaC2+ 2H2O → Ca(OH)2+ C2H2

(acetylene)
2. From alkyl halides 2. From alkyl halides 2. From alkyl halides

3.From carboxylic acid 3. From Alcohol by dehydration --------------

(Decarboxylation)

4. Wurtz reaction. -------------------- -----------------------

D. Physical Properties of hydrocarbons:

1. The melting and boiling point increases with increase in molecular mass and decreases
with increase in branching
2. They are insoluble in water but soluble in covalent solvents such as benzene, CCl4, CS2
etc.
3. They are lighter than water

E. Chemical properties of Alkanes:

1. Substitution reaction (e.g. halogenation)

2. Combustion: 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:.

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4. Aromatization or reforming:

5. Pyrolysis:

F. Chemical properties of Alkenes:

1. Addition of hydrogen: Alkenes add hydrogen in presence of finely divided Ni, Pd or Pt to form
alkanes.

2. Addition of halogen: Alkenes add halogen (Cl2 orBr2) to form vicinal dihalides.
CH2 = CH2 + X2 → CH2X-CH2X
This reaction is used as a test for unsaturation.
CH2 = CH2 + Br2 → CH2Br-CH2Br
Orange colourless
3. Addition of HBr to unsymmetrical alkenes (Markovnikov Rule):
“When an unsymmetrical reagent is added to an unsymmetrical alkene, the negative part of
the addendum (adding molecule) gets attached to the carbon containing lesser number of hydrogen
atoms”

4. Anti-Markovnikov addition:
In the presence of peroxide, addition of HBr to unsymmetrical alkenes takes place
against Markovnikov rule. This is known as peroxide effect or Kharash effect

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.

6. Oxidation:
When oxidized using cold and dilute aqueous solution of potassium permanganate
(KMnO4) [commonly called Baeyer’s reagent], alkenes give vicinal glycols. This reaction is also
used as a test for unsaturation.

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7. Ozonolysis :
Ozonolysis of alkenes involves the addition of ozone molecule to alkene to form ozonide,
and then cleavage of the ozonide by Zn-H2O to smaller molecules. This reaction is highly useful
in detecting the position of the double bond in alkenes or other unsaturated compounds.

G. Chemical properties of Alkynes:

1. Acidic character:
1-alkynes are acidic in nature due to the greater s character (50%) of the sp hybridised
orbitals and hence the hydrogen atom is removed as H+.
CH≡CH + Na → CH≡C-Na+ + ½ H2
(sod. acetylide)
2. Addition reactions:
a) Addition of Dihydrogen.

b) Addition of Halogen.

c) Addition of Hydrogen halide.

d) Addition of water.

3. Polymerization Reaction:
a) Linear polymerisation:

b) Cyclic polymerisation:

H. Aromatic hydrocarbons (Arenes):

Most of the aromatic compounds have pleasant smell (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.

99
 i) Structure of Benzene: 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 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.

a) Resonance structures 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.

b) 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 a 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.

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:

100
 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.

ii) Aromaticity:

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 no. of

delocalised π electrons =10 and so on.

Example for some aromatic compounds are:

I. Preparation of Benzene:

1. Decarboxylation of aromatic acids:

2. Reduction of phenol: Phenol is reduced to benzene by passing its vapours over

heated zinc dust.

J. Reactions of Benzene:
i) Electrophilic Substitution Reactions:
These are reactions in which a weak electrophile is replaced by a strong electrophile.

a) Nitration:

101
b) Halogenation:

c) Sulphonation:

d) Friedel-Craft’s reaction:
➢ Friedel-Craft’s Alkylation reaction:

a) Friedel-Craft’s Acylation reaction:

ii) Addition Reactions

1. Addition of H2:

2. Addition of halogen:

iii) Combustion:

K. Directive influence of a functional group in mono-substituted benzene:

Mono-substituted 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. There are two types of substituents – ortho and para directing groups and meta
directing groups.

i) Ortho and para directing groups: Example for such groups are –OH, –NH2, –NHR,

-NHCOCH3, –OCH3, –CH3, –C2H5 etc. Generally, ortho-para directing groups are
activating groups, since they increase the electron density on benzene ring.

102
 ii) Meta directing groups: Examples are –NO2, –CN, –CHO, –COR, –COOH, –COOR, –
SO3H, etc. These groups direct the incoming group to meta position are called meta directing
groups. They are generally deactivating groups, since they reduce the electron density on
benzene ring.

L. Carcinogenicity and toxicity:

Benzene and polynuclear hydrocarbons containing more than two benzene rings fused
together are toxic and said to possess cancer producing (carcinogenic) property. Such
polynuclear hydrocarbons are formed on incomplete combustion of organic materials like
tobacco, coal and petroleum. They enter into human body and undergo various biochemical
reactions and finally damage DNA and cause cancer.

Some of the highly carcinogenic hydrocarbons are given below:

M. Reaction Map of Ethyne (Acetylene):

103
Reaction map of Benzene:

N. Mechanism of Reaction of hydrocarbons:

Mechanis of Chlorination of methane:

Chain Initiation step :

ii) Chain Propagation step:

iii) Termination:

104
Mechanism of Markovnikov rule:

Mechanism of Anti-Markovnikov’s addition reaction:

Mechanism of Electrophilic substitution of Benzene:

105