Lesson 4 – Chemical Bonds

Chemical Bond
The force that holds different atoms in a molecule is called chemical bond.
• Octet Rule
Atoms of different elements take part in chemical combination in order to complete their octet or to
attain the noble gas configuration.
• Valence Electrons
It is the outermost shell electron which takes part in chemical combination.
• Facts Stated by Kossel in Relation to Chemical Bonding

— In the periodic table, the highly electronegative halogens and the highly electro-positive alkali
metals are separated by noble gases.
— Formation of an anion and cation by the halogens and alkali metals are formed by gain of electron
and loss of electron respectively.
— Both the negative and positive ions acquire the noble gas configuration.
— The negative and positive ions are stabilized by electrostatic attraction Example,

• Modes of Chemical Combination

— By the transfer of electrons: The chemical bond which formed by the complete transfer of one or
more electrons from one atom to another is termed as electrovalent bond or ionic bond.
— By sharing of electrons: The bond which is formed by the equal sharing of electrons between one
or two atoms is called covalent bond. In these bonds electrons are contributed by both.
— Co-ordinate bond: When the electrons are contributed by one atom and shared by both, the bond
is formed and it is known as dative bond or co-ordinate bond.

• Ionic or Electrovalent Bond

Ionic or Electrovalent bond is formed by the complete transfer of electrons from one atom to
another. Generally, it is formed between metals and non-metals. We can say that it is the
electrostatic force of attraction which holds the oppositely charged ions together.
The compounds which is formed by ionic or electrovalent bond is known as electrovalent
compounds. For Example, ,

(i) NaCl is an electrovalent compound. Formation of NaCl is given below:

Na+ ion has the configuration of Ne while Cl– ion represents the configuration of Ar.
(ii) Formation of magnesium oxide from magnesium and oxygen.

Electrovalency: Electrovalency is the number of electrons lost or gained during the formation of an
ionic bond or electrovalent bond.
• Factors Affecting the Formation of Ionic Bond
(i) Ionization enthalpy: As we know that ionization enthalpy of any element is the amount of energy
required to remove an electron from outermost shell of an isolated gaseous atom to convert it into
cation.
Hence, lesser the ionization enthalpy, easier will be the formation of a cation and have greater
chance to form an ionic bond. Due to this reason alkali metals have more tendency to form an ionic
bond.

For example, in formation of Na+ ion I.E = 496 kJ/mole

While in case of magnesium, it is 743 kJ/mole. That’s why the formation of positive ion for sodium is
easier than that of magnesium.
Therefore, we can conclude that lower the ionization enthalpy, greater the chances of ionic bond
formation.
(ii) Electron gain enthalpy (Electron affinities): It is defined as the energy released when an isolated
gaseous atom takes up an electron to form anion. Greater the negative electron gain enthalpy, easier
will be the formation of anion. Consequently, the probability of formation of ionic bond increases.
For example. Halogens possess high electron affinity. So, the formation of anion is very common in
halogens.

(iii) Lattice energy or enthalpy: It is defined as the amount of energy required to separate 1 mole of
ionic compound into separate oppositely charged ions.
Lattice energy of an ionic compound depends upon following factors:

(i) Size of the ions: Smaller the size, greater will be the lattice energy.
(ii) Charge on the ions: Greater the magnitude of charge, greater the interionic attraction and hence
higher the lattice energy.
• General Characteristics of ionic Compounds
(i) Physical’State: They generally exist as crystalline solids, known as crystal lattice. Ionic compounds
do not exist as single molecules like other gaseous molecules e.g., H2 , N2 , 02 , Cl2 etc.
(ii) Melting and boiling points: Since ionic compounds contain high interionic force between them,
they generally have high melting and boiling points.
(iii) Solubility: They are soluble in polar solvents such as water but do not dissolve in organic solvents
like benzene, CCl4etc.

(iv) Electrical conductivity: In solid state they are poor conductors of electricity but in molten state or
when dissolved in water, they conduct electricity.
(v) Ionic reactions: Ionic compounds produce ions in the solution which gives very fast reaction with
oppositely charged ions.
For example,

• Covalent Bond—Lewis-Langmuir Concept

When the bond is formed between two or more atoms by mutual contribution and sharing of
electrons, it is known as covalent bond.
If the combining atoms are same the covalent molecule is known as homoatomic. If they are
different, they are known as heteroatomic molecule.
For Example,
• Lewis Representation of Simple Molecules (the Lewis Structures)
The Lewis dot Structure can be written through the following steps:

(i) Calculate the total number of valence electrons of the combining atoms.
(ii) Each anion means addition of one electron and each cation means removal of one electron. This
gives the total number of electrons to be distributed.
(iii) By knowing the chemical symbols of the combining atoms.
(iv) After placing shared pairs of electrons for single bond, the remaining electrons may account for
either multiple bonds or as lone pairs. It is to be noted that octet of each atom should be completed.

• Formal Charge
In polyatomic ions, the net charge is the charge on the ion as a whole and not by particular atom.
However, charges can be assigned to individual atoms or ions. These are called formal charges.
It can be expressed as
• Limitations of the Octet Rule
(i) The incomplete octet of the central atoms: In some covalent compounds central atom has less
than eight electrons, i.e., it has an incomplete octet. For example,

Li, Be and B have 1, 2, and 3 valence electrons only.

(ii) Odd-electron molecules: There are certain molecules which have odd number of electrons the
octet rule is not applied for all the atoms.

(iii) The expanded Octet: In many compounds there are more than eight valence electrons around
the central atom. It is termed as expanded octet. For Example,
• Other Drawbacks of Octet Theory
(i) Some noble gases, also combine with oxygen and fluorine to form a number of compounds like
XeF2 , XeOF2 etc.
(ii) This theory does not account for the shape of the molecule.

(iii) It does not give any idea about the energy of The molecule and relative stability.
• Bond Length
It is defined as the equilibrium distance between the centres of the nuclei of the two bonded atoms.
It is expressed in terms of A. Experimentally, it can be defined by X-ray diffraction or electron
diffraction method.

• Bond Angle
It is defined as -the angle between the lines representing the orbitals containing the bonding –
electrons.
It helps us in determining the shape. It can be expressed in degree. Bond angle can be experimentally
determined by spectroscopic methods.
• Bond Enthalpy
It is defined as the amount of energy required to break one mole of bonds of a particular type to
separate them into gaseous atoms.
Bond Enthalpy is also known as bond dissociation enthalpy or simple bond enthalpy. Unit of bond
enthalpy = kJ mol-1
Greater the bond enthalpy, stronger is the bond. For e.g., the H—H bond enthalpy in hydrogen is
435.8 kJ mol-1.
The magnitude of bond enthalpy is also related to bond multiplicity. Greater the bond multiplicity,
more will be the bond enthalpy. For e.g., bond enthalpy of C —C bond is 347 kJ mol -1 while that of C
= C bond is 610 kJ mol-1.
In polyatomic molecules, the term mean or average bond enthalpy is used.

• Bond Order
According to Lewis, in a covalent bond, the bond order is given by the number of bonds between two
atoms in a molecule. For example,
Bond order of H2 (H —H) =1
Bond order of 02 (O = O) =2
Bond order of N2 (N = N) =3
Isoelectronic molecules and ions have identical bond orders. For example, F2 and O22- have bond
order = 1. N2, CO and NO+ have bond order = 3. With the increase in bond order, bond enthalpy
increases and bond length decreases. For example,

• Resonance Structures
There are many molecules whose behaviour cannot be explained by a single-Lew is structure, Tor
example, Lewis structure of Ozone represented as follows:
Thus, according to the concept of resonance, whenever a single Lewis structure cannot explain all
the properties of the molecule, the molecule is then supposed to have many structures with similar
energy. Positions of nuclei, bonding and nonbonding pairs of electrons are taken as the canonical
structure of the hybrid which describes the molecule accurately. For 0 3, the two structures shown
above are canonical structures and the III structure represents the structure of 03 more accurately.
This is also called resonance hybrid.

Some resonating structures of some more molecules and ions are shown as follows:

• Polarity of Bonds
Polar and Non-Polar Covalent bonds
Non-Polar Covalent bonds: When the atoms joined by covalent bond are the same like; H2, 02, Cl2, the
shared pair of electrons is equally attracted by two atoms and thus the shared electron pair is
equidistant to both of them.
Alternatively, we can say that it lies exactly in the centre of the bonding atoms. As a result, no poles
are developed and the bond is called as non-polar covalent bond. The corresponding molecules are
known as non-polar molecules.
For Example,

Polar bond: When covalent bonds formed between different atoms of different electronegativity,
shared electron pair between two atoms gets displaced towards highly electronegative atoms.
For Example, in HCl molecule, since electronegativity of chlorine is high as compared to hydrogen
thus, electron pair is displaced more towards chlorine atom, thus chlorine will acquire a partial
negative charge (δ–) and hydrogen atom have a partial positive charge (δ+) with the magnitude of
charge same as on chlorination. Such covalent bond is called polar covalent bond.

• Dipole Moment
Due to polarity, polar molecules are also known as dipole molecules and they possess dipole
moment. Dipole moment is defined as the product of magnitude of the positive or negative charge
and the distance between the charges.

• Applications of Dipole Moment

(i) For determining the polarity of the molecules.
(ii) In finding the shapes of the molecules.
For example, the molecules with zero dipole moment will be linear or symmetrical. Those molecules
which have unsymmetrical shapes will be either bent or angular.
(e.g., NH3with μ = 1.47 D).
(iii) In calculating the percentage ionic character of polar bonds.
• The Valence Shell Electron Pair Repulsion (VSEPR) Theory
Sidgwick and Powell in 1940, proposed a simple theory based on repulsive character of electron pairs
in the valence shell of the atoms. It was further developed by Nyholm and Gillespie (1957).
Main Postulates are the following:
(i) The exact shape of molecule depends upon the number of electron pairs (bonded or non bonded)
around the central atoms.
(ii) The electron pairs have a tendency to repel each other since they exist around the central atom
and the electron clouds are negatively charged.
(iii) Electron pairs try to take such position which can minimize the rupulsion between them.
(iv) The valence shell is taken as a sphere with the electron pairs placed at maximum distance.
(v) A multiple bond is treated as if it is a single electron pair and the electron pairs which constitute
the bond as single pairs.
• Valence Bond Theory
Valence bond theory was introduced by Heitler and London (1927) and developed by Pauling and
others. It is based on the concept of atomic orbitals and the electronic configuration of the atoms.
Let us consider the formation of hydrogen molecule based on valence-bond theory.
Let two hydrogen atoms A and B having their nuclei NA and NB and electrons present in them are
eA and eB .
As these two atoms come closer new attractive and repulsive forces begin to operate.
(i) The nucleus of one atom is attracted towards its own electron and the electron of the other and
vice versa.
(ii) Repulsive forces arise between the electrons of two atoms and nuclei of two atoms. Attractive
forces tend to bring the two atoms closer whereas repulsive forces tend to push them apart.
• Orbital Overlap Concept
According to orbital overlap concept, covalent bond formed between atoms results in the overlap of
orbitals belonging to the atoms having opposite spins of electrons. Formation of hydrogen molecule
as a result of overlap of the two atomic orbitals of hydrogen atoms is shown in the figures that
follows:

Stability of a Molecular orbital depends upon the extent of the overlap of the atomic orbitals.
• Types of Orbital Overlap
Depending upon the type of overlapping, the covalent bonds are of two types, known as sigma (σ )
and pi (π) bonds.
(i) Sigma (σ bond): Sigma bond is formed by the end to end (head-on) overlap of bonding orbitals
along the internuclear axis.
The axial overlap involving these orbitals is of three types:
• s-s overlapping: In this case, there is overlap of two half-filled s-orbitals along the internuclear axis
as shown below:

• s-p overlapping: This type of overlapping occurs between half-filled s-orbitals of one atom and half
filled p-orbitals of another atoms.
• p-p overlapping: This type of overlapping takes place between half filled p-orbitals of the two
approaching atoms.

(ii) pi (π bond): π bond is formed by the atomic orbitals when they overlap in such a way that their
axes remain parallel to each other and perpendicular to the internuclear axis.The orbital formed is
due to lateral overlapping or side wise overlapping.

• Strength of Sigma and pf Bonds

Sigma bond (σ bond) is formed by the axial overlapping of the atomic orbitals while the π-bond is
formed by side wise overlapping. Since axial overlapping is greater as compared to side wise. Thus,
the sigma bond is said to be stronger bond in comparison to a π-bond.
Distinction between sigma and n bonds
• Hybridisation
Hybridisation is the process of intermixing of the orbitals of slightly different energies so as to
redistribute their energies resulting in the formation of new set of orbitals of equivalent energies and
shape.
Salient Features of Hybridisation:
(i) Orbitals with almost equal energy take part in the hybridisation.
(ii) Number of hybrid orbitals produced is equal to the number of atomic orbitals mixed,
(iii) Geometry of a covalent molecule can be indicated by the type of hybridisation.
(iv) The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
Conditions necessary for hybridisation:
(i) Orbitals of valence shell take part in the hybridisation.
(ii) Orbitals involved in hybridisation should have almost equal energy.
(iii) Promotion of electron is not necessary condition prior to hybridisation.
(iv) In some cases filled orbitals of valence shell also take part in hybridisation.
Types of Hybridisation:
(i) sp hybridisation: When one s and one p-orbital hybridise to form two equivalent orbitals, the
orbital is known as sp hybrid orbital, and the type of hybridisation is called sp hybridisation.
Each of the hybrid orbitals formed has 50% s-characer and 50%, p-character. This type of
hybridisation is also known as diagonal hybridisation.

(ii) sp2 hybridisation: In this type, one s and two p-orbitals hybridise to form three equivalent
sp2 hybridised orbitals.
All the three hybrid orbitals remain in the same plane making an angle of 120°. Example. A few
compounds in which sp2 hybridisation takes place are BF3, BH3, BCl3 carbon compounds containing
double bond etc.

(iii) sp3 hybridisation: In this type, one s and three p-orbitals in the valence shell of an atom get
hybridised to form four equivalent hybrid orbitals. There is 25% s-character and 75% p-character in
each sp3 hybrid orbital. The four sp3 orbitals are directed towards four corners of the tetrahedron.

The angle between sp3 hybrid orbitals is 109.5°.

A compound in which sp3 hybridisation occurs is, (CH4). The structures of NH2 and H20 molecules can
also be explained with the help of sp3 hybridisation.
• Formation of Molecular Orbitals: Linear Combination of Atomic Orbitals (LCAO)
The formation of molecular orbitals can be explained by the linear combination of atomic orbitals.
Combination takes place either by addition or by subtraction of wave function as shown below.
The molecular orbital formed by addition of atomic orbitals is called bonding molecular orbital while
molecular orbital formed by subtraction of atomic orbitals is called antibonding molecular orbital.
Conditions for the combination of atomic orbitals:
(1) The combining atomic orbitals must have almost equal energy.
(2) The combining atomic orbitals must have same symmetry about the molecular axis.
(3) The combining atomic orbitals must overlap to the maximum extent.
• Types of Molecular Orbitals
Sigma (σ) Molecular Orbitals: They are symmetrical around the bond-axis.
pi (π) Molecular Orbitals: They are not symmetrical, because of the presence of positive lobes above
and negative lobes below the molecular plane.
• Electronic configuration and Molecular Behaviour
The distribution of electrons among various molecular orbitals is called electronic configuration of
the molecule.
• Stability of Molecules

• Bond Order
Bond order is defined as half of the difference between the number of electrons present in bonding
and antibonding molecular orbitals.
Bond order (B.O.) = 1/2 [Nb-Na]
The bond order may be a whole number, a fraction or even zero.
It may also be positive or negative.
Nature of the bond: Integral bond order value for single double and triple bond will be 1, 2 and 3
respectively.
Bond-Length: Bond order is inversely proportional to bond-length. Thus, greater the bond order,
smaller will be the bond-length.
Magnetic Nature: If all the molecular orbitals have paired electrons, the substance is diamagnetic. If
one or more molecular orbitals have unpaired electrons, it is paramagnetic e.g., 02 molecule.
• Bonding in Some Homonuclear (Diatomic) Molecules
(1) Hydrogen molecule (H2): It is formed by the combination of two hydrogen atoms. Each hydrogen
atom has one electron in Is orbital, so, the electronic configuration of hydrogen molecule is

This indicates that two hydrogen atoms are bonded by a single covalent bond. Bond dissociation
energy of hydrogen has been found = 438 kJ/mole. Bond-Length = 74 pm
No unpaired electron is present therefore,, it is diamagnetic.
(2) Helium molecule (He2): Each helium atom contains 2 electrons, thus in He2 molecule there would
be 4 electrons.
The electrons will be accommodated in σ1s and σ*1s molecular orbitals:
• Hydrogen Bonding
When highly electronegative elements like nitrogen, oxygen, flourine are attached to hydrogen to
form covalent bond, the electrons of the covalent bond are shifted towards the more electronegative
atom. Thus, partial positive charge develops on hydrogen atom which forms a bond with the other
electronegative atom. This bond is known as hydrogen bond and it is weaker than the covalent bond.
For example, in HF molecule, hydrogen bond exists between hydrogen atom of one molecule and
fluorine atom of another molecule.
It can be depicted as

• Types of H-Bonds
(i) Intermolecular hydrogen bond (ii) Intramolecular hydrogen bond.
(i) Intermolecular hydrogen bond: It is formed between two different molecules of the same or
different compounds. For Example, in HF molecules, water molecules etc.
(ii) Intramolecular hydrogen bond: In this type, hydrogen atom is in between the two highly
electronegative F, N, O atoms present within the same molecule. For example, in o-nitrophenol, the
hydrogen is in between the two oxygen atoms.
 Lesson 3- Periodic Table
Genesis of Periodic Classification Dobereiner’s Triads
In 1829, Dobereiner arranged certain elements with similar properties in groups of three in such a
way that the atomic mass of the middle element was nearly the same as the average atomic masses
of the first and the third elements. A few triads proposed by him are listed.

Limitations of Dobereiner’s Trids

The triads given by Dobereiner were helpful in grouping some elements with similar characteristics
together, but he could not arrange all the elements known at that time into triads.
• Newlands’ Law of Octaves
John Newlands proposed the law of octaves by stating that when elements are arranged in order of
increasing atomic masses, every eighth element has properties similar to the first. Newlands called it
law of octaves because similar relationship exists in the musical notes also.
This can be illustrated as:

Limitations of Newlands’ Law of Octaves

(i) This classification was successful only up to the element calcium. After that, every eighth element
did not possess the same properties as the element lying above it in the same group.
(ii) When noble gas elements were discovered at a later stage, their inclusion in the table disturbed
the entire arrangement.
• Mendeleev’s Periodic Table
Mendeleev’s Periodic Law: The physical and chemical properties of the elements are a periodic
function of their atomic masses.
Mendeleev arranged the elements known at that time in order of increasing atomic masses
and this arrangement was called periodic table.
Elements with similar characteristics were present in vertical rows called groups. The horizontal
rows were known as periods.
Description of Mendeleev’s Periodic Table
(i) In the periodic table, the elements are arranged in vertical rows called groups and horizontal rows
known as periods.
(ii) There are nine groups indicated by Roman Numerals as I, II, III, IV, V, VI, VII, VIII and zero. Group
VIII consists of nine elements which are arranged in three triads. The zero group contains elements
belonging to inert gases or noble gases and elements present have zero valency.

(iii) There are seven periods (numbered from 1 to 7) or, horizontal rows in the Mendeleev’s periodic
table.
Importance of Mendeleev’s Periodic Table
(i) This made the study of the elements quite systematic in the sense that if the properties of one
element in a particular group are known, those of others can be pridicted.
(ii) This helped to a great extent in the discovery of these elements at a later stage.
(iii) Mendeleev corrected the atomic masses of certain elements with the help of their expected
positions and properties.
Defects in Mendeleev’s Periodic Table
(i) Hydrogen has been placed in group IA along with alkali metals. But it also resembles halogens of
group VII A in many properties. Thus, its position is the Mendeleev’s periodic table is controversial.
(ii) Although the elements in the Mendeleev’s periodic table have been arranged in order of their
atomic masses, but in some cases the element with higher atomic mass precedes the element with
lower atomic mass.

(iii) We know that the isotopes of an element have different atomic masses but same atomic number.
Since, periodic table has been framed on the basis of increasing atomic masses of the elements,
different positions must have been allotted to all the isotopes of a particular element.
(iv) According to Mendeleev, the elements placed in the same group must resemble in their
properties. But there is no similarity among the elements in the two sub-groups of a particular
group.
(v) In some cases, elements with similar properties have been placed in different groups.
(vi) Lanthanoids and actinoids were placed in two separate rows at the bottom of the periodic table
without assigning a proper reason.

(vii) No proper explanation has been offered for the fact that why the elements placed in group show
resemblance in their properties.
• Modern Periodic Law
Physical and chemical properties of the elements are the periodic function of their atomic numbers.
• Present Form of the Periodic Table (Long form of Periodic Table)
The long form of periodic table, also called Modem Periodic Table, is based on Modern periodic law.
In this table, the elements have been arranged in order of increasing atomic numbers.
• Nomenclature of Elements with Atomic No. more than 100

• Structural Features of the Periodic Table

Groups
The long form of periodic table also consists of the vertical rows called groups. There are in all 18
groups in the periodic table. Unlike Mendeleev periodic table, each group is an independent group.
Characteristics of groups:
(i) All the elements present in a group have same general electronic configuration of the atoms.
(ii) The elements in a group are separated by definite gaps of atomic numbers (2, 8, 8,18, 18,32).

(iii) The atomic sizes of the elements in group increase down the group due to increase the number
of shells.
(iv) The physical properties of the elements such as m.p., b.p. density, solubility etc., follow a
systematic pattern.
(v) The elements in each group have generally similar chemical properties.
Periods
Horizontal rows in a periodic table are known as periods.
There are in all seven periods in the long form of periodic table.
Characteristics of periods:
(i) In all the elements present in a period, the electrons are filled in the same valence shell.
(ii) The atomic sizes generally decrease from left to right.
s-Block Elements
General electronic configuration: ns1-2 Characteristics of s-block elements:
(i) All the elements are soft metals.
(ii) They have low melting and boiling points.
(iii) They are highly reactive.
(iv) Most of them impart colours to the flame.
(v) They generally form ionic compounds.
(vi) They are good conductors of heat and electricity. p-Block Elements
General electronic configuration: ns2np1-6
Characteristics of p-block elements:
(i) The compounds of these elements are mostly covalent in nature.
(ii) They show variable oxidation states.
(iii) In moving from left to right in a period, the non-metallic character of the elements increases.
(iv) The reactivity of elements in a group generally decreases downwards.

(v) At the end of each period is a noble gas element with a closed valence shell ns2 np6 configuration.
(vi) Metallic character increases as we go down the group.
d-Block Elements
General electronic configuration: (n -1) d1-10 ns0-2
The d-block elements are known as transition elements because they have incompletely filled d-
orbitals in their ground state or in any of the oxidation states.

Characteristics of d-block elements:

(i) They are all metals with high melting and boiling points.
(ii) The compounds of the elements are generally paramagnetic in nature.
(iii) They mostly form coloured ions, exhibit variable valence (oxidation states).
(iv) They are of tenly used as catalysts.
f-Block Elements
General electronic configuration: (n – 2) f1-14 (n -1) d0-1 ns2
They are known as inner transition elements because in the transition elements of d-block, the
electrons are filled in (n – 1) d sub-shell while in the inner transition elements of f-block the filling of
electrons takes place in (n – 2) f subshell, which happens to be one inner subshell. Characteristics of
f-Block elements:

(i) The two rows of elements at the bottom of the Periodic Table, called the Lanthanoids Ce (Z = 58) –
Lu (Z = 71) and Actinoids Th (Z = 90) – Lr (Z = 103).
(ii) These two series of elements are called Inner Transition Elements (f-Block Elements).
(iii) They are all metals. Within each series, the properties of the elements are quite similar.
(iv) Most of the elements pf the actinoid series are radio-active in nature.
• Metals
(i) Metals comprise more than 78% of all known elements and appear on the left side of the Periodic
Table.
(ii) Metals are solids at room temperature.
(iii) Metal usually have high melting and boiling points.
(iv) They are good conductors of heat and electricity.
(u) They are malleable and ductile.
• Non-metals
(i) Non-metals are located at the top right hand side of the Periodic Table.
(ii) Non-metals are usually solids or gases at low temperature with low melting and boiling points.
(iii) They are poor conductors of heat and electricity.
(iv) The non-metallic character increases as one goes from left to right across the Periodic
Table.
(v) Most non-metallic solids are brittle and are neither malleable nor ductile.
• Metalloids
The elements (e.g., silicon, germanium, arsenic, antimony and tellurium) show the characteristic, of
both metals and non-metals. These elements are also called semimetal.
• Noble Gases
– These are the elements present in group 18.
– Eash period ends with noble gas element.
– All the members are of gaseous nature and because of the presence of all the occupied filled
orbitals, they have very little tendency to take part in chemical combination.
– These are also called inert gases.
• Representative Elements
The elements of group 1 (alkali metals), group 2 (alkaline earth metals) and group 13 to 17 constitute
the representative elements. They are elements of s-block and p-block.
• Transition Elements
The transition elements include, all the d-block elements and they are present in the centre of the
periodic table between s and p-block elements.
• Inner Transition Elements
Lanthanoids (the fourteen elements after Lanthanum) and actinides (the fourteen elements after
actinium) are called inner transition elements. They are also called f-block elements.
The elements after uranium are also called transuranic elements.
• Periodic Trends in Properties of Elements
Trends in Physical Properties
Atomic Radii: It is defined as the distance from the centre of the nucleus to the outermost shell
containing the electrons. Depending upon whether an element is a non-metal or a metal, three
different types of atomic radii are used. These are:
(a) Covalent radius (b) Ionic Radius (c) van der Waals radius (d) Metallic radius.

(a) Covalent Radius: It is equal to half of the distance between the centres of the nuclei of two atoms
held together by a purely covalent single bond.
(b) Ionic Radius: It may be defined as the effictive distance from the nucleus of an ion upto which it
has an influence in the ionic bond.
(c) van der Waals Radius: Atoms of Noble gases are held together by weak van der Waals forces of
attraction. The van der Waals radius is half of the distance between the centre of nuclei of atoms of
noble gases.
(d) Metallic Radius: It is defined as half of the intemuclear distance between the two adjacent metal
ions in the metallic lattice.
• Variation of Atomic Radius in the Periodic Table
Variation in a Period: Along a period, the atomic radii of the elements generally decreases from left
to right.

Variation in a group: The atomic radii of the elements in every group of the periodic table increases
as we move downwards.
• Ionic Radius
The ionic radii can be estimated by measuring the distances between cations and anions in ionic
crystals.
In general, the ionic radii of elements exhibit the same trend as the atomic radii.

Cation: The removal of an electron from an atom results in the formation of a cation. The radius of
cation is always smaller than that of the atom.
Anion: Gain of an electron leads to an anion. The radius of the anion is always larger than that ‘ of
the atom.
Isoelectronic Species: Some atoms and ions which contain the same number of electrons, we call
them isoelectronic species. For example, O2-, F–, Na+ and Mg2+ have the same number of electrons
(10). Their radii would be different because of their different nuclear charges.
• Ionization Enthalpy
It is the energy required to remove an electron from an isolated gaseous atom in its ground state.
M (g) + I.E ——->M+ (g) + e–
The unit of ionization enthalpy is kJ mol-1 and the unit of ionization potential is electron volt per
atom.
Successive Ionization Enthalpies
If a gaseous atom is to lose more than one electron, they can be removed one after the other i.e., in
succession and not simultaneously. This is known as successive ionization enthalpy (or potential).
• Variation of Ionization Enthalpies in the Periodic Table:
Variation of Ionization Enthalpy Along a Period
Along a period ionization enthalpies are expected to increase in moving across from left to the right,
because the nuclear charge increases and the atomic size decreases.
Variation of Ionization Ethalpy in a Group
The ionization enthalpies of the elements decrease on moving from top to the bottom in any group.
The decrease in ionization enthalpies down any group is because of the following factors.
(i) There is an increase in the number of the main energy shells (n) in moving from one element to
the other.
(ii) There is also an increase in the magnitude of the screening effect due to the gradual increase in
the number of inner electrons.

• Electron Gain Enthalpy

Electron Gain Enthalpy is the energy released when an electron is added to an isolated gaseous atom
so as to convert it into a negative ion. The process is represented as:

For majority of the elements the electron gain enthalpy is negative. For example, the electron gain
enthalpy for halogens is highly negative because they can acquire the nearest noble gas configuration
by accepting an extra electron.
In contrast, noble gases have large positive electron gain enthalpies because the extra electron has to
be placed in the next higher principal quantum energy level thereby producing highly unstable
electronic configuration.
Successive Electron Gain Enthalpies
We have studied that electrons from a gaseous atoms are lost in succession (i.e., one after the
other). Similarly, these are also accepted one after the other, i.e., in succession. After the addition of
one electron, the atom becomes negatively charged and the second electron is to be added to a
negatively charged ion. But the addition of second electron is opposed by electrostatic repulsion and
hence the energy has to be supplied for the addition of second electron. Thus the second electron
gain enthalpy of an element is positive.
For example, when an electron is added to oxygen atom to form O– ion, energy is released. But when
another electron is added to 0- ion to form O2- ion, energy is absorbed to overcome the strong
electrostatic repulsion between the negatively charged 0– ion and the second electron being added.
Thus, first electron gain enthalpy:

Factors on which Electron Gain Enthalpy Depends

(i) Atomic size: As the size of an atom increases, the distance between its nucleus and the incoming
electron also increases and electron gain enthalpy becomes less negative,
(ii) Nuclear charge: With the increase in nuclear charge, force of attraction between the nucleus and
the incoming electron increases and thus electron gain enthalpy becomes more negative.
(iii) Symmetry of the Electronic Configuration: The atoms with symmetrical configuration (having
fully filled or half filled orbitals in the same sub-shell) do not have any urge to take up extra electrons
because their configuration will become unstable.
In that case the energy will be needed and electron gain enthalpy (Δ eg H) will be positive. For
example, noble gas elements have positive electron gain enthalpies.
Variation of Electron Gain Enthalpy Across a Period
Electron gain ethalpy becomes more negative with increase in the atomic number across a period.
Variation of Electron Gain Enthalpy in a Group
Electron gain enthalpy becomes less negative as we go down a group.

• Electronegativity
A qualitative measure of the ability of an atom in a chemical compound to attract shared electrons to
itself is called electronegativity. Unlike ionization enthalpy and electron gain enthalpy, it is not a
measurable quantity.
However, a number of numerical scales of electronegativity of elements viz, Pauling scale, Milliken-
Jaffe scale, Allred Kochow scale have been developed. The electronegativity of any given element is
not constant; it varies depending on the element to which it is bound.
Across a Period
Electronegativity generally increases across a period from left to right.
In a Group
It decreases down a group.

• Periodic Trends in Chemical Properties along a Period

(i) Metallic character: Decrease across a period maximum on the extreme left (alkali metals).
(ii) Non-metallic character: Increasess along a period. (From left to right).
(iii) Basic nature of oxides: Decreases from left to right in a period.
(iv) Acidic nature of oxides: Increases from left to right in a period.
• Variation from Top to Bottom on Moving Down a Group
(i) Metallic character. Generally increases because increase in atomic size and hence decrease in the
ionizatiort energy of the elements in a group from top to bottom.
(ii) Non-metallic character. Generally decreases down a group. As electronegativity of elements
decreases from top to bottom in a group.
(iii) Basic nature of oxides. Since metallic character or electropositivity of elements increases in going
from top to bottom in a group basic nature of oxidise naturally increases.
(iv) Acidic character of oxides. Generally decreases as non-metallic character of elements decreases
in going from top to bottom in a group.
(v) Reactivity of metals. Generally increases down a group. Since tendency to lose electron increases.
(vi) Reactivity of non-metals. Generally decreases down the group, Higher the electro-negativity of
non-metals, greater is their reactivity. Since electronegativity of non-metals in a group decreases
from top to bottom, their reactivity also decreases.
• Anomalous Properties of Second Period Elements
The first element of each of the group 1 (lithium) and 2 (beryllium) and group 13-17 (boron to
fluorine) differs in many respect from the other members of their respective groups. For example,
lithium unlike other alkali metals, and beryllium unlike other alkaline earth metals
form compounds which have significant covalent character; the other members of these groups, pre-
dominatly form ionic compounds.
It has been observed that some elements of the second period show similarities with the elements
of the third period placed diagonally to each other, though belonging to different groups.
For example,

This similarity in properties of elements placed diagonally to each other is called diagonal
relationship.
• Mendeleev’s Periodic Law. Physical and chemical properties of elements are periodic function of
their atomic masses.
• Modem Periodic Law. Physical and chemical properties of the elements are periodic function of
their atomic numbers.
• Groups. There are 18 groups. These are vertical rows.
• Periods. There are 7 periods. These are horizontal rows.
• Representative Elements. The S and P block of elements are known as representative elements.
• Transition Elements. They are also called d-block elements. They have general electronic
configuration (n – 1) d1-10 ns0-2.
• Inner Transition Elements. Lanthanoids (the fourteen elements after Lanthanum) and actinides
(the fourteen elements after actinium) are called inner transition elements. General electronic
configuration is (n – 2) f1-14(n – 1) d0-1 ns2.
They are also called f-block elements.
• Metals. Present on the left side of the periodic table. Comprise more than 78% of the known
elements.
• Non-metals. Mostly located on the right hand side of the periodic table.
• Metalloids. Elements which line as the border line between metals and non-metals (e.g., Si, Ge, As)
are called metalloids or semimetals.
• Atomic Radii and Ionic Radii, increase down the group decrease along the period.
• Ionization Enthalpy. Increases along the period and decreases down the group.
• Noble Gas Elements. Elements with symmetrical configuration are chemically inert in nature.
• Electric Nuclear Charge. Z = Nuclear charge – Screening constant.
• Electronegativity. Increases along a period decreases down the group,
• Chemical Reactivity. Chemical reactivity is highest at the two extremess of a period and lowest in
the centre.
• Oxides of Elements. Oxides formed of the Elements on the left are basic and of elements
on the right are acidic in nature.
Oxides of elements in the centre are amphoteric or neutral.