Notes for grade 11th students

Unit- One: Atomic structure and periodic properties of the elements

1.1 Introduction

-In the early philosophers were thought that all materials are made up of four things called elements:

Earth, air, water and fire.

-Indivisible and indestructible atoms are the basic components of all matter in the universe.

-The word atom is derived from Greek word ―atomos‖ meaning indivisible.

1.2 Dalton’s and modern atomic theory

Atomic theory is a statement that interprets the facts about atoms.

1.2.1 Dalton's atomic theory

1. All substances are made up of tiny, indivisible particles called atoms.

2. Atoms of the same element are identical in shape, size, mass and other properties.

3. Atoms of different elements are different in all respects.

4. Atom is the smallest unit that takes part in chemical combinations.

5. Atoms combine with each other in simple whole number ratios to form compound atoms called molecules.

6. Atoms cannot be created, divided or destroyed during any chemical or physical change.

Exercise:

1. List down the postulates of Dalton that continued to have significance (retained in modern Atomic theory)

2. Describe the limitations of Dalton‘s Atomic theory

1.2.2 postulates of modern Atomic theory

1. Elements are made up of small particles called atoms

2. Atoms cannot be created or destroyed during ordinary chemical reactions

3. All atoms of the same element have the same Atomic number but may vary mass number due to the
presence of different isotopes

4. Atoms of different elements are different

5.atoms combine in small whole number to form compounds

1.3. EARLY EXPERIMENS TO CHAACTERIZE THEATOM

-Moving away from the idea of indivisible particles to divisible once

-Gradually revealed the complex structure of the atom

1.3.1 Discovery of the electron

J.J. Thomson discovered he electron using cathode-rays discharge tube experiment

Fig 1:Cathod rays rotating light paddel weel between cathode and anode

-Led to the plum pudding model where electrons were embedded in a positively charged sphere
Fig 2: Thomson’s plum pudding model of an atom

properties of cathode rays:

 They travel in a straight line from the cathode and cast shadows of metallic
 Cathode-rays consists of negatively charged particles and that electros are the constituents of all
matter

Limitations of Thomson’s atomic model

- failed to explain the stability of an atom

- failed to account for the position of the nucleus in an atom

- failed to explain the scattering of alpha particles by thin metal foils

1.3.2 Radioactivity and the discovery of the nucleus

Radioactivity: is the spontaneous emission of energy from the unstable nuclei of certain elements sch as
uranium or radium.

Atoms consist of a nucleus containing protons and neutrons, surrounded by electrons. When the nucleus of
an atom is unstable, it can undergo radioactive decay, a process where it releases energy in the form of
radiation to become more stable.

There are three main types of radiation emitted during radioactive decay:

-Alpha () radiation/particles: positively charged particles.

-Beta () radiation/particles: high-speed electrons emitted from the nucleus.

-Gamma () radiation/rays: high-energy electromagnetic radiation emitted from the nucleus.
-This process occurs when an unstable atomic nucleus loses energy by mitting radiation in the form of
particles (alpha, beta) or electromagnetic waves (gamma rays)

-Radio decay is a random process but can be measured by a substances half-life

-half-life the time it takes for half of its atoms to decay

( )

-Radioactivity is used in medicine, energy generation and scientific research.

Discovery of the nucleus

Rutherford‘s Alpha Scattering Experiment

His experiment, directed high energy streams of α-particles from a radioactive source at a thin sheet (100 nm
thickness) of gold.
In order to study the deflection caused to the α-particles, he placed a fluorescent zinc supplied screen around
the thin gold foil.

-Using α-particles Through the gold foil experiment, Rutherford discovered the nucleus of an atom

-From this experiment, while most α-particles did pass through, a small fraction were deflected at large
angles, and some even bounce back.

-This le to new model of the atom, with a small, denes, positively charged nucleus at its center, containing
most of the atom‘s mass.

Observations of Rutherford’s Alpha Scattering Experiment

The observations made by Rutherford led him to conclude that:

1. A major fraction of the α-particles bombarded towards the gold sheet passed through the sheet
without any deflection, and hence most of the space in an atom is empty.

2. Some of the α-particles were deflected by the gold sheet by very small angles, and hence the positive
charge in an atom is not uniformly distributed. The positive charge in an atom is concentrated in a
very small volume.

3. Very few of the α-particles were deflected back, that is only a few α-particles had nearly 180o angle
of deflection. So the volume occupied by the positively charged particles in an atom is very small as
compared to the total volume of an atom.
Based on the above observations and conclusions, Rutherford proposed the planetary atomic model structure
of elements. According to the Rutherford atomic model:

4. The positive charge and most of the mass of an atom is concentrated in an extremely small volume.
He called this region of the atom as a nucleus.

5. Rutherford‘s model proposed that the negatively charged electrons surround the nucleus of an atom.
He also claimed that the electrons surrounding the nucleus revolve around it with very high speed in
circular paths. He named these circular paths as orbits.

6. Electrons being negatively charged and nucleus being a densely concentrated mass of positively
charged particles are held together by a strong electrostatic force of attraction.

Based on the above observations and conclusions, Rutherford proposed the atomic structure of elements.
According to the Rutherford atomic model:

1. The positive charge and most of the mass of an atom is concentrated in an extremely small volume.
He called this region of the atom as a nucleus.

2. Rutherford‘s model proposed that the negatively charged electrons surround the nucleus of an atom.
He also claimed that the electrons surrounding the nucleus revolve around it with very high speed in
circular paths. He named these circular paths as orbits.

3. Electrons being negatively charged and nucleus being a densely concentrated mass of positively
charged particles are held together by a strong electrostatic force of attraction.
Fig3: Rutherford’s model of the structure of atom
Rutherford‘s Atomic Model could wonderfully explain the presence of a positively charged nucleus and the
presence of electrons outside the nucleus in an atom.

Limitations of Rutherford's model of the atom include

 The model failed to explain the stability of atoms.
 The arrangement of electrons in a circular path was not defined.
 Any particle that is moving in a circular path would undergo acceleration and radiates energy. Thus, the
revolving electron would lose energy and finally fall into the nucleus.
 The model does not account for the location or distribution of electrons.
1.3.3 The discovery of netron

How neutons discoveed?

The neutron was also discovered by alpha-particle scattering experiments by James Chadwick.

When beryllium metal is irradiated with alpha rays, a strongly penetrating radiation is obtained from the
metal. this penetrating radiation consists of neutral particles, called neutrons.

The neutron is a nuclear particle having a mass almost identical to that of the proton but with no electric
charge. The mass of a neutron, mn= 1.67493 × 10–27 kg, which is about 1840 times the mass of an electron.
1.4 make-up of the nucleus

-All Atomic nuclei are made up of two kinds of particles: protons and neutrons

- Most of the mass of an atom is concentrated in the nucleus assuming the mass of an electron to be almost
zero.

1.4.1 Subatomic particles

The three main sub-atomic particles are: electrons, protons and neutrons.

All atoms have two regions.

 The nucleus: a very small region located at the center of an atom.

 all Atomic nuclie are made up of two kinds of particles:protons and neutrons.
 Most of the mass of an atom is concentrated in the nucleus assuming the mass of an electron to be
negligible or almost zero.
 Surrounding the nucleus (electron cloud): the region occupied by electrons.very large when compared
with the size of the nucleus.
 The radius of an atom is the distance from the center of the nucleus to the outer portion of electron
cloud.This is about 1×10^-10 m= 100pm= 0.1nm

Atomic number (Z) : the number of protons present in the nucleus (Moseley1913).

 Atomic number an element = number of protons.

 Table.1: properties of sub atomic particles

 1.4.2
Atomic mass and isotopes
Mass Number (A) :Sum of the number of protons and neutrons present in the nucleus in an atom.

It is also known as the total number of nucleons in the atoms nucleus.

-Mass Number (A)= Ps + Ns

Example 1: what is the mass number of an atom of helium that contains 2 neutrons?

 No of protons = 2, no of neutrons = 2
 Mass Number (A)= number of protons + number of neutrons
 Mass Number (A)= 2 + 2 =4
 Example 2: what is the number of electrons, protons and neutrons for an atom 226 83Ra.
 Question: What is the difference b/n mass number and atomic mass?

Isotopes:

-these are the atoms of the same element having the same atomic number but different mass number(due to
different number of neutrons).e g , ,

Q. Why atoms of different elements have different properties?

B/c of arrangements and the number of sub-atomic particles.

-Many isotopes accurate naturally. But few are most stable and common.

Unstable isotopes:

How is radioactive decay exist?

radioactive decay exists with Unstable isotopes

 Example:Uraniu,radiu,rodon and thorium

-Different isotopes of an element generally have the same chemical and physical properties.

b/c they have the same number of protons

-For most elements other than hydrogen, isotopes are named for their mass number.

-Example: C atom with 6, 7 & 8 neutrons called C-12, C-13 & C-14 respectively
 Isobars: are the atoms of different elements having the same mass number but different atomic number.e
g and
 Isoelectronic species: are species which have the same number of electrons.
 Example: and
Q. Why all atoms are Neutral? B/c all atoms contain equal numbers of protons and electrons

Example 2: what is the number of electrons, protons and neutrons for an atom

Q : What is the difference b/n mass number and atomic mass?

If an element consists of n isotopes, of relative masses A1,A2, ... An and fractional abundances f1,f2,f3,...fn, then
the average relative atomic mass(A) of the element is given by:

= + + A3 +.... +

The general Nuclear symbol of an atom Is expressed by

1.5 Electromagnetic radiation and atomic spectra

1.5.1 Electromagnetic radiation

In 1873, James Clerk Maxwell proposed that light consists of electromagnetic waves.

EMR is the emission and transmission of energy in the form of electromagnetic waves.
Main energy levels of an electron:Different orbits in which electrons revolve are called energy levels or

stationary states.

Fig 1.5: The electric field and magnetic field components of EMR

-Electromagnetic waves have three primary characteristics:

Wavelength(λ): is the distance the wave travels during one cycle . It is expressed in meters (m) and often,
for very short wavelengths, in nanometers (nm), picometers (pm), or angstrom (Å).

frequency (ν,): is the number of cycles the wave undergoes per second and is expressed in units

of l/second (1/s; also called hertz, Hz). and

Fig.6: the frequency of waves

speed(C): the product of its wavelength and its frequency is called the speed of light.

-It depends on the type of wave and the nature of the medium through which it is traveling (for example, air,
water, or a vacuum).

νλ

-In a vacuum, electromagnetic waves travel at 3 ´108m/s, which is a physical constant

-EMR comes in a broad range of frequencies called the electromagnetic spectrum

(Figure 1.7).

-A rainbow is an example of a continuous spectrum.

-Different wavelengths in visible light have different colors from red (λ = 750 nm) to violet (λ= 380 nm).

-Radiation provides an important means of energy transfer.

-For instance, the energy from the Sun reaches the Earth mainly in the form of visible and ultraviolet

radiation. The glowing coals of a fireplace transmit heat energy by infrared radiation. In microwave ovens,
microwave radiation is used to heat water in foods, causing the food to cook quickly.

Fig 1.7: The lectromagnetic spectrum

Exampl1: Ethiopian National Radio, Addis Ababa station broadcasts its AM signal at a

frequency of 2400 kHz. What is the wavelength of the radio wave expressed in meters?

Solution: = λν

Exercise: Mekelle FM radio station, broadcasts electromagnetic radiation at a frequency of 104.4 MHz What
is the wavelength of the radio waves, expressed in meters?

1.5.2 The quantum theory and photon

quantum theory: explains how matter and energy behave at small scales such as atoms and sub atomic
particle.

-Is concerned with the rules that govern the gain or loss of energy from an object.

-Accordingly max plank proposed that a hot glowing object could emit (or absorb) only certain amount of
energy. i.e. energy is not emitted continuously (it is quantized).

-This means the particles can only absorb or emit energy in fixed amount.

- energy is always emitted or absorbed in integral multiples of hν; for example, hν, 2hν, 3hν,etc.

The energy E of a single quantum is given by: Each of these small

“packets” of energy is called a quantum.

Photon: is a fundamental particle of light and other forms of EMR.

It is massless, elementary particle that carries energy proportional to its frequency

The Photoelectric Effect:

Refers to the phenomena where electrons are emitted from a material, typically a metal, when it absorbs light
or EMR.
-Einstein proposed that light consists of discrete energy (photons), and when a photon hits an electron, it
transfers energy to the electron, allowing it to escape the metal‘s surface.

The photoelectric effect is a phenomenon in which electrons are ejected from the surface of certain metals
exposed to light of at least a certain minimum frequency, called the threshold frequency,νo

- The threshold frequency represents the minimum energy required to remove the electron from the metal‘s surface. the threshold frequency represents the

minimum energy required to remove the electron from the metal‘s surface.

A photon with energy less than Eo(ν< νo)cannot remove an electron, or a light with a frequency less than the
νo produces no electrons. On the other hand, if a light has , the energy in excess of that required to
remove the electron is given to the electron as kinetic energy (KE):

Mathematically: ⁄

where

Wok function of the material (metal) is measured in joules or eV and ⁄ is kinetic energy of the
ejected electron?

Intensity of light is a measure of the number of photons present in a given part of the beam: a greater
intensity means that more photons are available to release electrons (as long as ν> νo for the radiation).

Example: Light of frequency is incident on a metal surface with a work function of 2 eV.
Calculate the kinetic energy and velocity of the ejected electron

Solution: Given information,

J, Kg ,

Then calculate photon energy J

Einstein, In his theory of relativity in 1905, Einstein derived the famous equation:
Where E is energy, mis mass, and c is speed of light. The main significance of Equation 1.7 is that energy
has mass. Then, the apparent mass of a photon of light with wavelength is given by:

1.5.2 Atomic spectra

Why the spectrums of atoms for every element are unique?

Every element on the periodic table contains a different number of electrons in its neutral state. Each atom as
its ow unique set of energy levels, so the spectra lines serve as a ―fingerprint‖ for that atom.

Atomic or line spectra are produced from the emission of photons of electromagnetic radiation (light).

Different kinds of spectrum are observed when an electric discharge, or spark, passes through a gas such as
hydrogen. The electric discharge is an electric current that excites, or energizes, the atoms of the gas.

The atoms then emit the absorbed energy in the form of light as the electrons return to lower energy states.

When a narrow beam of this light is passed through a prism, we do not see a continuous spectrum, or
rainbow, as sunlight does. Rather, only a few colors are observed, displayed as a series of individual lines.
This series of lines is called the element‘s atomic spectrum or emission spectrum.

The wavelengths of these spectral lines are characteristic of the element producing them, and used for their
identification. For example, the emission (line) spectrum of hydrogen atom is show in the Figure below
Figure 1.11: The hydrogen line spectrum, containing only a few discrete wavelengths

Changes in energy ( ) between discrete energy levels in hydrogen will produce only
certain wavelengths of emitted light, as shown in Figure-xxx

Figure 1.12: A change between two discrete energy levels emits a photon of ligh

1.5.4 The Bohr model of hydrogen atom

-Bohr explained why the orbiting electron does not radiate energy as it moves around the nucleus.

He introduced the fundamental idea that the absorption and emission of light by hydrogen atoms was due to
energy changes of the electrons within the atoms. The fact that only certain frequencies are absorbed or
emitted by an atom tells us that only certain energy changes are possible. Thus, energy changes in an atom
are quantized.

Bohr used Planck‘s and Einstein‘s ideas about quantized energy and proposed the following assumptions:

1. The electron in a hydrogen atom travels around the nucleus in a circular orbit.

2. The energy of the electron in an atom is proportional to its distance from the nucleus. The further an
electron is from the nucleus, the more energy it has.

3. Only limited number of orbits with certain energies are allowed. This means, the orbits are quantized.

4. The only orbits that are allowed are those for which the angular momentum of the electron is an integral
multiple of h/2π.

5. As long as an electron stays in a given orbital, it neither gains or losses energy.

That means, the atom does not change its energy while the electron moves within an orbit.

6. The electron moves to a higher energy orbit only by absorbing energy in the form of light, and emitting
light when it falls to a lower energy orbit. The energy (photon) of the light absorbed or emitted is exactly
equal to the difference between the energies of the two orbits.

-The radii, r, of the permitted orbits or energy levels for an atom of hydrogen atom are:

, ( )

For instance, for n= 1 This is the first Bohr radius. The larger the values of n, the further the
electron from the nucleus.
Figure 1.13: Bohr’s energy levels of a hydrogen atom

These levels can be thought of as concentric circles around the nucleus, with each successive circle holding
electrons at a higher energy than the one before.

represents the first (innermost) energy level, the second, and so on.

He also showed that the energies that an electron in hydrogen atom can occupy are given by:

The energy of a free electron is given a value of zero.

When which corresponds to the most stable energy state and termed as ground state or ground level,
which refers to the lowest energy state of an atom. it is possible to calculate the energy of a single electron in
a ground state or excited state, or the energy change when an electron moves between two energy levels from
this Bohr‘s equation.

The stability of the hydrogen electron diminishes for

-A hydrogen electron for which n is greater than 1 is said to be in an excited state, which is higher in energy
than the ground state
Example:

The absorptions and emissions in line spectra correspond to the transfer of the electron from one orbit to
another.

Energy must be absorbed for the electron to move from one orbit to another one having a bigger radius.
Whereas, energy is emitted when an electron moves from the higher orbital energy level, n i, to the lower
orbital nf energy level.

Thus, the change in energy, ∆E, is the difference in the energy between the final and the initial state electron:
Where ni and nf represent quantum numbers for initial and final states respectively.

When ∆E is positive, indicating that the system has absorbed energy. But, ∆E is
negative and this corresponds to emission of energy.

Example 1.7

Each spectral line in the emission spectrum corresponds to a particular transition in a hydrogen atom are
illustrated in the Figure 1.14 below
Figure 1.14: The emission spectrum of a hydrogen atom

- The energy levels are labeled with their principal quantum numbers,

The emission spectrum of hydrogen includes a wide range of wavelengths from the infrared to the ultraviolet
(Table 1.2)

Table 1.2: The various series in atomic hydrogen emission spectrum

- For a larger orbit radius (i.e. a higher atomic energy level), the further the electron drops, the greater is the
energy (higher v, shorter λ) of the emitted photon.

1.5.5 Limitations of the Bohr model

The model has several limitations:

• It doesn't explain the atomic spectra of more complicated atoms and ions, even that of helium, the next
simplest element.

• It doesn't explain about further splitting of spectral lines in the hydrogen spectra on application of a
magnetic field.
• It considers electrons to have both known radius and orbit, which is impossible according to Heisenberg's
uncertainly principle.

1.5.6 The wave-particle duality of matter and energy

Is proposed by Louis de Broglie: if energy is particle-like, perhaps matter is wave-like

-By combining Einstein‘s( ) with Planck‘s equation (

⁄ ……….x

According to this Equation x, matter and energy show both wave and particulate properties. This dual
character of matter and energy is known as the wave-particle duality.

Example:

Exercise: Calculate the wavelength (in nm) of a photon emitted when a hydrogen atom undergoes a
transition from to

1.6 The quantum mechanical model of the atom

-quantum mechanics is a different view from classical physics on how electrons are arranged about the
nucleus in the atom.
Mainly, it depends on two central concepts: the wave behavior of matter and the uncertainty principle

1.6.1 The Heisenberg’s principle

-It stating that it is not possible to know with great certainty both an electron‘s position and its
momentum(where )at the same time.Mean that if ∆p is the uncertainty in the momentum and ∆x is
the uncertainty of the position of the electron, then:

In simpler terms, if we know precisely where a particle is, we cannot know precisely where it has come from
or where it is going. If we know precisely how a particle is moving, we cannot know precisely where it is.

1.6.2 The quantum numbers

-Are parameters that describe the distribution of electrons in the atom, its fundamental nature such as: the
size, energy, shape and position of the orbitals.

Erwin Schrödinger (1927), suggested that an electron or any other particle exhibiting wave-like properties
can be described by a mathematical equation called a wave function (psi, ψ) and this provides information
about the energy of electrons and their position.

-ψ2 gives the probability of finding an electron in a certain region of a space.

-The probability of the electron being at a definite location (in a rapid motion within a given region of
space around the nucleus called an orbital) can be calculated but cannot determine the precise position of
an electron.

-Thus, an electron can be considered as a particle that can rapidly move from place to place, behaving like an
―electron cloud‖ whose density varies within the orbital.

-There are four types of quantum numbers: principal, angular momentum, magnetic and spin.

1. The principal quantum number (n) describes the main energy level, or shell, an electron occupies. It may
be any positive integer, ,etc.
- It describes the size and energy of the shell in which the orbital resides and it is analogous to the energy
levels in Bohr‘s model.

-With the increase in the value of ‗n‘, the number of allowed orbital increases and are given by ‗n2‘.

-Maximum number of electrons present in any shell (given by the formula 2n2)

-All the orbitals of a given value of ‗n‘ constitute a single shell of atom and are represented by the following
letters.

n 1 2 3 4……

Shell K L M N……

2. The angular momentum quantum number (ℓ) designates the shape of the atomic orbitals. Within a shell
different sublevels or subshells are possible, each with a characteristic shape.
It takes values from 0 to n-1. Orbitals of the same but differentℓare said to belong to different subshells.
It is also called azimuthal quantum number or subsidiary quantum number. A given energy level, n, has
total number of orbitals. For example, in n = 4, ℓ has values of 0, 1, 2, and 3. Each value of ℓ
corresponds to an orbital label and an orbital shape.

The following letters are usually used to denote the values of ℓ:

3. The magnetic quantum number (mℓ) is also called the orbital-orientation quantum number. It has
integral values between -ℓand ℓ, including 0. The value of mℓ is related to the orientation of the orbital in
space relative to the other orbitals in the atom. The number of possible mℓvalues or orbitals for a
givenℓvalue is 2ℓ + 1.
4. The electron spin quantum number (ms) refers to the spin of an electron and the orientation of the
magnetic field produced by this spin. For every set of n, ℓ, and mℓvalues, ms can take the value +½or -½.
Each atomic orbital cannot accommodate more than two electrons, one with and another with

Example 1:

Exercise 1: What are the values of n and ℓ for the and subshells?

Exercise 2: Write the subshell notations that correspond to and

1.6.3 The shape of atomic orbitals

-Boundary surface diagram: three-dimensional aspects of the orientation of the atomic orbitals that
encloses the highest probability (about 90%) of the total electron density in an orbital.
-S- orbital: spherically symmetrical shape. Whose values are . The subshell is with one orbital

Regardless of their principal quantum numbers, all s orbitals are spherical.

-The 1s orbital is the smallest, the 2s orbital is larger than 1s and so on.

Figure1.10: The three S-orbitals

-P- orbital: dumb bell-shaped. Whose values are .

-The subshell is with three orbitals

-The three p orbitals are designated as px, y and pz.. Two lobes of each p orbital lie along a line with the nucleus at their center

Figure1.11: The three p-orbitals

d- Orbital: double dumb bell-shaped. Whose values are

-The subshell is with five orbitals

-The special orientations of d orbitals are much more complex in

shape than p orbitals.

Figure1.12: different distribution of the five d-orbitals

-f- orbital: more complex shape of orbitals.

-Whose values are . The subshell is with seven orbitals

Generally the four quantum numbers can be tableted as follows.

1.7 Electronic configurations and orbital diagrams

Electron configuration of an element: describes how electrons are distributed among the given energy
levels or shells. It is the systematic arrangement of electrons in the various shells or orbitals in an atom.

Maximum Electron Capacity

A main energy level's electron capacity is determined by the formula: 2n2.

-The first energy level ( ) can hold a maximum of 2(12) = 2 electrons.

-Following the formula, the second energy level, can hold a maximum of 8es

For , the thired energy level can hold a maximum of 32 electrons

Valence shell: the last shell or outermost shell from the nucleus with electron

Penultimate shell: the nearest shell to the

Valence electrons: electrons reside at the outer shell

There are three basic principles governing the distribution of electrons among atomic orbitals.

1. Aufbau (building up) Principle: filling lower-energy orbitals before higher- energy orbitals.

Thus, the order in which the orbitals are filled is as follows: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d,
6p, 7s
Figure 1.13: Increasing order of filling orbitals.

2. Hund’s Principle:

Equal energy orbitals (degenerate orbitals) are each occupied by a single electron before the second electrons
of opposite spin enters the orbital. In other words, each of the three 2p orbitals (2px, 2py and 2pz) will hold a
single electron before any of them receives a second electron

3. Pauli’s Exclusion Principle:

No two electrons can have the same four quantum numbers. That means, they must differ in at least one of
the four quantum numbers.

-Each orbital contains a maximum of two electrons.

These two electrons must have opposite values for the spin, which is generally indicated by showing
N.B Sometimes there are exceptions to the Aufbau principle like chromium and copper

Why the observed electron configuration is different from the expected once for those atoms?

May be, the half-filled 3d subshell of chromium (3d5) and the fully filled 3d subshell of copper (3d10) lends a
special stability to the electron configurations.

As summery, the electron configuration of different atoms can be principled via the three rules using
example of, C has z=6 and its electronic configuration is: 1s2, 2s2, 2p2

1.7.1 Ground state electronic configuration of the elements

-Describes the distribution of the electrons among atomic orbitals in the atom.
-Two general methods are used to denote electron configurations.

A, The subshell (sublevel) notation:

-Uses numbers to designate the principal energy levels and the letters s, p, d and f to identify the sublevels.
The designation can be written as

-For example, the ground state electron configuration of H (Z=1) is

-To avoid writing the inner-level electrons, the configuration is often abbreviated as [noble gas]

-In the electron configuration of an atom, the electrons in the outermost principal quantum level of an
atom are called valence electrons. On the other hand, the inner electrons are also known as core electrons.

-Valence electrons are the most important electrons to chemists since they are involving in bonding

Table 1.3: Ground state electron configurations of some atoms

B, through an orbital diagram:

-consists of a rectangular box (or circle, or just a line) for each orbital available in a given energy level, with
an arrow indicating the electron‘s presence and its direction of spin.

-The orbital diagrams for the first ten elements are:

1.8 Electronic configuration and Periodic Properties of Elements
How does the electron configuration of an element give information about the period and group it is in?
1.8.1 The modern periodic table

The modern periodic table tells us that, if we arrange the elements in order of increasing atomic number, we
periodically encounter elements that have similar chemical and physical properties. The vertical columns are
referred to as groups or families, and the horizontal rows are called periods.

-Elements with similar valence-shell electron configurations fall in the same group of the periodic table. For
A-group elements, the group number corresponds to the number of electrons in the principal shell of
highest quantum number.

The period number is the same as the highest number of principal shell containing electrons (the outer
shell).The division of the periodic table into s, p, d and f blocks greatly assists in the assignment of probable
electron configurations.

-Elements in a group have similar chemical and physical properties, and those within a period have
properties that change progressively across the table.

1.8.2 Classification of the elements

- Elements can be divided into representative, transition, and inner transition elements based on the type
of subshell being filled.

Representative or main group elements: These consist of all s- and p-block elements.
The chemical properties of the representative elements are determined by the number of valence electrons in
their atoms.

Transition elements: These are d-block elements. There are four series of transitional elements, 3d, 4d, 5d
and c6d depending on the energy levels of d-orbitals.

Inner transition elements: These are the f-block elements. There are two series of f-block elements, 4f and
5f series called lanthanides and actinides, respectively.

The periodic table is unable to include the inner transition elements in its main frame. They have been
allotted the same single place in the periodic table though their electronic configurations are not identical.
Besides, the variation in their properties is not much.

Figure 1.14: the modern periodic table

-Several groups of elements have common names that are used so frequently they should be learned.

--The group IA elements, except H, are referred to as alkali metals, and the group IIA elements are called
the alkaline earth metals. The Group VIIA elements are called halogens, which mean ―salt formers,‖ and
the Group VIIIA elements are called noble (or rare) gases.
1.8.2 Periodic properties

-Certain atomic properties vary periodically, when atoms are considered in terms of increasing atomic
number (nuclear charge).

-The properties and trends considered are like atomic radii, ionization energies, electron affinities,
electronegativity, and metallic character.

a) Atomic radii or atomic size:

-As we move across the periodic table, atoms become smaller due to increasing effective nuclear
charges, ,as we move from left to right across a period in the periodic table,

-Atomic radii of representative elements decrease as a proton is added to the nucleus and an electron is added
to a particular shell.

-The effective nuclear charge, experienced by an electron in an outer shell is less than the actual nuclear
charge, Z. This is because the attraction of outer-shell electrons by the nucleus is partly counterbalanced by
the repulsion of these outer-shell electrons by electrons in inner shells. This concept of a screening, or
shielding, effect helps us understand many periodic trends in atomic properties.

-Consider an atom of lithium; it has two electrons in a filled shell, 1s2, and one electron in the 2s orbital, 2s1.
The electron in the 2s orbital is fairly effectively screened from the nucleus by the two electrons in the filled
1s orbital, so the 2s electron does not ―feel‖ the full 3 charge of the nucleus, the effective nuclear charge,
, experienced by the electron in the 2s orbital:

Example: , =11-10 = +1, , =12-10= +2, , =13-10= +3

b) Ionic Radii

Ionic Radii of metals always greater than the corresponding cations, because they lost electrons from shells
which reduced electron-electron repulsions.

Example; Mg (1.6 Ǻ) > Mg2+(0.85 Ǻ).

Simple negatively charged ions (anions) are always larger than the neutral atoms from which they are formed
because there is addition of extra electron to the shell which increased electron.

Example: Cl-(1.67 Ǻ) > Cl (1.1 Ǻ).

Both sizes of cations and anions decrease from left to right across a period whereas both cation and anion
sizes increase going down a group.

Isoelectronic ions: ions with the same number of core electrons. Na+, Mg+2, Al+3, F-, O2, N-3 all contain 10
electrons; all have the same electron configuration as Ne but, in terms of size,

N-3>O-2>F->Na+>Mg+2>Al+3;

-The ion with the greater number of protons in an isoelectronic series will be the smallest due to the greater
nuclear charge pulling the electrons in closer. I.e. radii decrease with increasing atomic number because of
increasing nuclear charge. is determined by slater rule. Slater rule is best method to calculate the correct
effective nuclear charge, .The respected values for screening/ shielding effect( )are:

a) For electrons With the same shell(same n shell)

b) For electrons With the n-1 shell,
c) For electrons With n-2 and less shells

In general:

Arrange the following ions in order of increasing ionic radii: (a) Ca2+, K+, Al3+ , (b) Se2-, Br-,Te2-

Answers: a) Al3+< Ca2+ < K+ , b) Br-< Se2-< Te2-

c) Ionization (potential) Energy

-Can be defined as the minimum amount of energy required to remove an electron from ground state (loosely
bounded) atom in gaseous state. It measures how outermost electrons held by the nucleus.

X (g) + IE → X+ (g) + e

The first ionization energy (IE1), also called first ionization potential, is the minimum amount of energy
required to remove the most loosely bound electron from an isolated gaseous atom to form an ion with a 1+
charge. Elements with low ionization energies (IE) lose electrons easily to form cations.

-Exceptions occur at Groups IIIA and VIA. The first ionization energies for the Group IIIA elements (B, Al,
Ga, In, Tl) are exceptions to the general horizontal trends. They are lower than those of the IIA elements in
the same periods because the IIIA elements have only a single electron in their outermost p orbitals. Less
energy is required to remove the first p electron than the second s electron from the outermost shell, because
the p orbital is at a higher energy (less stable) than an s orbital within the same shell (n value) Effective
nuclear charge, , increases going from left to right across a period. The increase in effective nuclear
charge causes the outermost electrons to be held more tightly, making them harder to remove. The first
ionization energies of the Group IIA elements (Be, Mg, Ca, Sr, Ba) are significantly higher than those of the
Group IA elements in the same periods. This is because the Group IIA elements have higher values and
smaller atomic radii. Thus, their outermost electrons are held more tightly than those of the neighboring IA
metals. It is harder to remove an electron from a pair in the filled outermost s orbitals of the Group IIA
elements than to remove the single electron from the half-filled outermost s orbitals of the Group IA
elements. The general left-to-right increase in IE1for each period is interrupted by a dip between Groups VA
(N, P, As, Sb, Bi) and VIA elements (O, S, Se, Te, Po).

Presumably, this behavior is because the fourth np electron in the Group VIA elements is paired with another
electron in the same orbital, so it experiences greater repulsion than it would in an orbital by itself. This
increased repulsion apparently outweighs the increase in , so the fourth np electron in an outer shell
(Group VIA elements) is somewhat easier to remove (lower ionization energy) than is the third np electron in
an outer shell (Group VA elements).

The first ionization energies therefore generally increase from left to right across the periodic table. The
order of ionization energies decreased as 3rd > > because it is too difficult to remove an
electron from cation specie.
In general ionization energy increase across the period since increase by one; the size of atoms decrease
which results the outermost electrons bound tightly with the nucleus.

General trends in ionization energy of group elements with position in the periodic table

d) Electron Affinity (EA):

The electron affinity (EA) of an element may be defined as the amount of energy released when an electron
is added to an isolated gaseous atom to form a negative charge.

X (g) + e- → X-(g) + EA

This process can be either endothermic or exothermic, depending on the element. You can see that many of
these elements have negative values of EA, which means that energy is released when the gaseous atom
accepts an electron. However, for some elements, energy is required for the atom to become negatively
charged and the value of their EA is positive.

Electron Affinity (EA): Energy is always required to bring a negative charge (electron) closer to another
negative charge (anion). So the addition of a second electron to anion to form an ion with a -2 charge is
always endothermic. Thus, electron affinities of anions are always positive.

X-(g) + e- → X2-(g) + EA

Most elements have no affinity for an additional electron and thus have an electron affinity (EA) equal to
zero. We can represent the electron affinities of helium and chlorine as

Halogens have ns2 -np5 electron configuration which are most electron affinities to form noble gas
configuration.
e) Electro-negativity (EN):

The electro-negativity (EN) of an element is a measure of the relative tendency of an atom to attract electrons
towards it when it is chemically combined with another atom.

Elements with high electro-negativities (non-metals) often gain electrons to form anions.

Example; F (4.0) > O (3.5) > Cl=N (3.0).

Elements with low electro-negativities (metals) often lose electron to form cations.

For the representative elements, electro-negativities usually increase from left to right across periods except
noble gas and decrease from top to bottom within groups.

Arrange the following elements in order of increasing electro-negativity? B, Na, F, O

Answer, Na< B< O< F

f) Metallic character:

Metallic character increases from top to bottom and decreases from left to right with respect to position in the
periodic table. Nonmetallic character decreases from top to bottom and increases from left to right in the
periodic table.

Figure 1.22: general schematic trends in metallic character of a group element with position in the periodic
table.

In modern periodic table, elements are arranged as the function of their atomic number.

Main group elements are elements contain s-block metals and p-block metal, metalloid and nonmetals. This
periodic table constructed with the columns (family) and the horizontal row (periods).
Periodicity is the variation of physical properties in periodic table such as atomic size, electronegativity,
ionization energy, metallic character and others as summarized below.

Advantages of Periodic Classification of the Elements

Some of the advantages of periodic classification of elements are:
1. The classification of elements is based on the atomic number, which is a fundamental property of an
element.
2. The reason for placing isotopes at one place is justified as the classification is on the basis of atomic
number.
3. It explains the periodicity of the properties of the elements and relates them to their electronic
configurations.
4. The position of the elements that were misfits on the basis of mass number (anomalous pairs like argon
and potassium) could be justified on the basis of atomic number.
5. The lanthanides and actinides are placed separately at the bottom of the periodic table.
6. The table is simple, systematic and easy way for remembering the properties of various elements as it is
based on the electronic configuration.
Chapter two: Chemical Bonding
2.1 Introduction
Bonding is the joining of at least two atoms to form a molecule or compound.

The electrons found in valence shell are the active portion of an atom during bonding.

What is chemical bond?

Chemical bonding is the force of attraction that binds atoms together in a molecule, or a crystal lattice.

Chemical bonding is formed by the interaction of outer most electrons between atoms.
A+ B A-B
2.1.1 Octet rule
Why atoms combined to form compounds, clusters, molecules/ polyatomic ions?

 In order to achieve a more stable electron configuration

 To attain lower potential energy

 T0 attain octet rule

How do atoms combined to form compounds, clusters, molecules or polyatomic ions? By:
 Transferring /losing of their valence electrons.

 Gaining of extra valence electrons

 Sharing of valence electrons

 Coordinating valence electrons

2.1.1 Types of Chemical Bonding

When atoms bond, their valence electrons are redistributed in ways that make the atoms more stable. The
way in which the electrons are redistributed determines the type of bonding.
There are three main types of chemical bonds: i, ionic, ii, covalent and metallic bonds
2.2 Ionic Bond (Electrovalent Bond)
Ionic Bond Is type of chemical bond that results from the electrostatic force of attraction between two
oppositely charged ions. As a result the bond is also called electrovalent bond
Why do elements form ions in certain chemical reactions?

Ionic bonds usually form between elements with large difference electronegativity( ), where one atom
(typically a metal) loses electrons, and the other (typically a nonmetal) gains them.

When large numbers of ions gather together, they form an ionic solid. The solid normally has a regular,
crystalline structure that allows for the maximum attraction of ions, given their particular sizes.

It is formed due to complete transfer of electrons from one atom to another by losing and gaining of electrons.
The atom that loses electrons will form a action and the atom that gains electrons will form an anion. These
oppositely charged ions come closer to each other due to electrostatic force of attraction and thus form an
ionic bond.
Any given ion tends to attract as many neighboring ions of opposite charge as possible.
Figure 2.1: Crystal model of sodium chloride
In general, an ionic bond is formed between two atoms that contain greater electronegativity difference. Most
of the time this bond is formed between a metal atom and a nonmetal atoms.
E.g. NaCl, KCl, MgF2, CaO and MgO
N.B: A key step to determine the likelihood formation of an ionic bond is to evaluate electronegativity
difference.
2.2.1 Lewis electron-dot symbols
A Lewis structure is a combination of Lewis symbols that represents either the transfer or the sharing of
electrons in a chemical bond.
A Lewis symbol consists of a chemical symbol to represent the nucleus and core (inner-shell) electrons of an
atom, together with dots placed around the symbol to represent the valence (outer-shell) electrons. For
example, the Lewis symbol for chlorine, which has the electron configuration, , is

Similarly the formation of sodium chloride from sodium and chlorine atoms can be represented as:

2.2.2 formation of ionic bond

The reason ionic substances exist at all is because of the enormous release of energy when the ions come
together and form a solid.
Consider just the electron-transfer process for the formation of lithium fluoride, which involves two steps:
1. A gaseous Li atom loses an electron (IE1):
 2. A gaseous F atom gains an electron lost by Li atom (EA):

Note that the two-step electron-transfer process by itself requires energy:

The total energy needed for ion formation is even greater than this because metallic lithium and diatomic
fluorine must first be converted to separate gaseous atoms, which also requires energy. Despite this, the
standard heat of formation (ΔHf°) of solid LiF is −617 kJ/mol; that is, 617 kJ is released when 1 mol of LiF(s)
forms from its elements. That is, there must be some exothermic energy component large enough to
overcome the endothermic steps. These are:
i. When 1 mol of Li+(g) and 1 mol of F−(g) form 1 mol of LiF (g):

ii. When the gaseous ions coalesce into a crystalline solid. That occurs because each ion attracts others of
opposite charge:

The negative of this value, 1050 kJ, is the lattice energy of LiF. The lattice energy (U) is the enthalpy change
(energy released) that occurs when 1 mole of ionic solid forms from its gaseous state ions. It indicates the
strength of ionic interactions, which influence melting point, hardness, solubility, and other properties.
Lattice Energies from the Born–Haber Cycle
Finding the lattice energy of an ionic solid by experiment is difficult. However, this quantity can be found
indirectly using the Born–Haber cycle. The reasoning is based on Hess‘s law, which states that an overall
reaction‘s enthalpy change is the sum of the enthalpy changes for the individual reactions that make it up:

or
= + + ⁄ + +
Consider the Born-Haber cycle for the formation of NaF. We think that solid sodium fluoride can be formed
from the elements by two different routes, as shown in Figure 2.2.
In one route, NaF(s) is formed directly from Na(s) and ½F2 (g); ΔHform° −411 kJ mol-1
Figure 2.2: Born–Haber cycle for NaF
Similarly, the Born-Haber cycle for the formation of NaCl, solid sodium chloride can be formed from the
elements by two different routes, as shown in Figure 2.3.
In one route, NaCl(s) is formed directly from Na(s) and ½Cl2(g); Δf_° −411 kJ mol-1

Figure 2.3: Born–Haber cycle for NaCl

The second route consists of the following five steps, along with the enthalpy change for each.
Note: Ionic solids exist only because the lattice energy exceeds the energy required for the electron transfer.
Example: For lithium, the enthalpy of sublimation is +161 kJ/ mole, and the first ionization energy is +520
kJ/ mole. The dissociation energy of fluorine is +154 kJ/ mole and the electron affinity of fluorine is –328 kJ/
mol. The lattice energy of LiF is –1047 kJ/ mol. Calculate the overall enthalpy change for the reaction Li(s) +
½F2(g) →LiF(s) ΔH° =?

Solution: = + + ⁄ + +

= +161 kJ/ mole +520 kJ/ mole + –328 kJ/ mole –1047 kJ/ mole

= -617 kJ/ mole

High lattice energy implies stronger electrostatic attractions between the ions in the crystal lattice, which
makes the solid harder to break apart and, thus more thermodynamically stable.
Exercise: Using the following data:
Enthalpy of sublimation of Ca = +178.2 kJ mol–1, Enthalpy of dissociation of Cl2 = +243.4 kJ mol–1,
Enthalpy of formation of CaCl2 = –795.8 kJ mol–1 First and second Ionization energies for Ca are +590 kJ
mol–1 and +1145 kJ mol–1 respectively. The electron affinity of Cl = –348.7 kJ mol–1.Determine the lattice
energy of CaCl2
B. Favorable condition for ionic bond formation
The formation of ionic bonding is influenced by various factors. Some of the major factors are
Low ionization energy of the metals: The lesser the ionization energy, the greater is the ease of the
formation of a cation. Thus, low ionization energy of metallic elements such as alkali and alkaline earth
metals favors the formation of an ionic bond.
High electro-affinity of the nonmetals: higher electron affinity favors the formation of an anion. Thus, low
ionization energy of a metal atom and high electron affinity of a non-metal atom facilitate the formation of an
ionic bond between them.
High lattice energy: When a cation and an anion come closer, they get attracted to each other due to the
electrostatic (coulombic) force of attraction. The electrostatic force of attraction between oppositely-charged
ions release a certain amount of energy and an ionic bond is formed. If the coulombic attraction forces are
stronger, then more energy gets released and a more stable or a stronger ionic bond is formed. Larger lattice
energy would favor the formation of an ionic bond. Lattice energy thus is a measure of coulombic attractive
force between the combining ions.
The lattice energy (U) of an ionic compound depends directly on the product of the ionic charges (q1 × q2),
and inversely on the distance (r) between them:

Where q1 and q2 are the charges on +ve and –ve ions respectively, and r is the distance between the charges
q1 and q2. Thus, small ions having a higher ionic charge will have larger lattice energy. If the total energy
released is more than that which is absorbed, then the formation of an ionic compound is favored.
The lattice energy is a measure of strength of ionic bonds (interactions), which influence the MP, hardness,
solubility and other properties.
High electro-negativity difference between metal and nonmetal atoms (which is ≥1.7 usually).
Note! Ionic compounds are usually formed when metal cations bond with non-metal anions. The only
common exception is ammonium ion which is not a metal, but it forms ionic compounds
2.2.3: Exceptions to octet rule in ionic compounds
Why does the octet rule work well only for the representative metals (Groups IA, IIA) and the non-metals,
but not for the transition elements?
There are certain exceptions to the octet rule (with ionic Compounds).
Less than Octet (Central Atom is Deficient of Electrons)
Ions of some elements which are near to helium in the periodic table do not obey the octet rule. The tendency
of these atoms (H, Li, Be and B) is to attain an arrangement of two electrons like the noble gas He, which is
also a stable configuration. The hydride ion (H–), lithium ion (Li+), beryllium ion (Be2+) and boron ion
(B3+) are isoelectronic with He.
Although atoms with less than an octet may be stable, they will usually attempt to form a fourth bond to get
eight electrons. For example BF3 is stable, but it will form BF4 − when possible.
More than Octet (18-Electron Rule)
The ions of some transition and post-transition elements do not usually obey the octet rule. For transition
metals, the 18-electron rule replaces the octet rule, due to the involvement of d orbitals of these atoms.
Why don’t the atoms of these elements lose electrons to achieve the noble-gas configurations of ns2np6?
Consider the electron configurations of the ions of the transition elements iron and zinc and the post-
transition elements gallium and tin.
Electron Configurations of Iron:
26Fe:
26 :
26 :
A stable ion of iron with valence shell electron configuration is 3s2 3p6 3d5 which is not isoelectronic with a
noble gas. Fe2+ is a well-known stable ion with a valence shell electron configuration 3s2 3p6 3d6 which is not
isoelectronic with any of the noble gases.
Electron configurations of zinc:

is also not isoelectronic with any of the noble gases.

Electron configurations of gallium:
The post-transition element gallium (Ga) loses electrons first from the 4p orbital and then from the 4s orbital
to from a ion as
On closely examining the electron configurations of Zn2+ and Ga3+, we will realize that ions have
completely-filled outer subshells and a noble gas core. Their valance electron configuration can be generally
represented as ns2np6nd10.
2.2.4 Properties of ionic compounds
High melting and boiling points: - due to strong electrostatic attraction of opposite charges
Hard but brittle:-ionic crystals are hard due to strong ionic bonds but are brittle because applying force
causes ions like charges to come in to contact, leading to repulsion and the crystal shattering.
Solubility in water: - are generally soluble in polar solvents like water because water molecules stabilize
the ions by surrounding them (hydration). They are insoluble in non-polar solvents like benzene.
Electrical conductivity:-Poor conductors in solid state and good conductors in aqueous or Melton state.
Formation of crystalline structures:- form regular, repeating patterns called ionic lattice and minimize
repulsion b/n ions
High enthalpy of formation: - the formation of ionic compounds release a large amount of energy due
to strong ionic bonds, making them thermodynamically stable
2.3 Covalent Bonds and Molecular geometry
Formation of Covalent Bonding (bond b/n non- metal and non- metal)
If the attractive forces are stronger than the repulsive forces, a covalent bond is formed, with the two atoms
held together and the two shared electrons occupying the region between the nuclei

Figure 2.4: Attractive and repulsive forces in a covalent H-H bond formation
What happens if the hydrogen atoms are too far apart? What if the hydrogen atoms are too close together?
There is an optimum distance between nuclei, called the bond length, where net attractive forces are
maximized and the H−H molecule is most stable. In the H2 molecule, the bond length is 74 pm. This is the
most stable arrangement (Figure 2.5).
Figure 2.5: Covalent bond formation in H2
A covalent bond is formed when a pair of electrons is shared between two atoms. Formation of a bond
always results in greater electron density between the nuclei.

Some examples of covalent molecules are HCl, H2S, C2H4, N2, CCl4, BCl3, H2O, NH3, SO2, PCl5, O3, etc.
Generally, substances that contain covalent bonds are called molecules.
Representation of Covalent Bonds (Drawing Lewis Structures)
The representation of covalent bonding through Lewis symbols and shared electron pairs is called a Lewis
structure. The Lewis structure for a hydrogen molecule formed from hydrogen atoms is:

The shared pairs of electrons in a molecule are called bonding pairs. The other electron pairs that stay with
on atom and are not shared are called non-bonding pairs or lone pairs.
In molecules such as O2, N2, and many others, the atoms share more than one pair of electrons, leading to the
formation of multiple covalent bonds.
For example, consider the formation of oxygen molecule (O2) from the oxygen atoms. The electronic
configuration of oxygen atoms is 2,6. Now each oxygen atom needs two electrons to complete its octet. The
two oxygen atoms share two electrons and complete their octet:
So these two pairs of shared electrons can be represented by two bonds between the oxygen atoms. An

oxygen molecule can be sown as follow:

The two oxygen atoms are said to be bonded together by two covalent bonds. Such a bond consisting of two
covalent bonds is also known as a double bond.
Steps to Writing a Lewis Formula:
1. Determine the total number of valence electrons. The total number of electrons for a molecule is the sum
of the valence electrons for each atom. For a polyatomic anion, which has one or more extra electrons,
add one electron for each unit of negative charge. For a polyatomic cation, which is missing one or more
electrons, subtract one electron for each unit of positive charge.
2. Write the skeletal structure. The most electropositive atom usually occupies the central position. Connect
bonded atoms with an electron-pair bond (a dash).
3. Place electron pairs around terminal atoms so that each (except hydrogen) has an octet. Assign any
remaining electrons as lone pairs around the central atom.
4. If at this stage, a central atom has fewer than eight electrons, a multiple bond(s) is likely. Move one or
more lone-pair of electrons from a terminal atom(s) to a region between it and the central atom to form a
double or a triple bond.
Example: Write the Lewis structure for nitrogen tri-fluoride (NF 3) in which all three F atoms are bonded to
the N atom.
Solution:
We follow the steps for writing Lewis structures.
Step 1: The outer-shell electron configurations of N and F are and , respectively. Thus,
there are 5 + (3 x 7), or 26, valence electrons to account for in NF3.
Step 2: The N atom is less electronegative than F, so in the skeletal structure of NF3, N goes in the center
with the more electronegative F atoms bonded to it.

Step 3: We draw a single covalent bond between N and each F, and complete the octets for the F atoms. We
place the remaining two electrons on N:
Coordinate-Covalent Bonding or dative bonds
Bonds formed when one atom donates both electrons (a lone pair) to another atom that has a vacant valence
orbital.
Example the ammonium ion (NH4 +) forms when the lone-pair electrons from the nitrogen atom of ammonia,
NH3, bond to H+. Such kind of bonds is called coordinate covalent bonds or dative bonds.

Some other examples of molecules which contain coordinate-covalent bonds include NH3, BCl3, H3O+ and
AlCl4−.
Resonance Structures
Resonance Structure is one of two or more valid Lewis structures that represent the same molecule or ion,
showing the delocalization of electrons. These structures differ only in the arrangement of electrons, not the
position of atoms, and together they describe the actual bonding as a hybrid of all possible forms. The
different structures used to represent the molecule or ion are called resonance forms or resonance
contributors or resonance structures.
Example: for ozone (O3)

Exercise:
What is the difference between a resonance structure and a resonance hybrid?
Solution: in case of ozone structures A&B are resonance structures and the remain9in above) is a resonance
hybrid
Some other molecule with resonance structures can be; C6H6, SO3, NO2F, HNO3, CO32−, NO2− etc.
2.3.3 Exceptions to the Octet rule in Covalent Bonding
Although many Lewis structures follow the octet rule, there are exceptions. There can be categorized into
three groups:
i. Less than octet (central atom is deficient of electrons):
Electron-deficient compounds are compounds in which an element has an incomplete octet.
The central atoms of such molecules have fewer than eight electrons (below octet).
This group consists of molecules containing central atoms from Group IIA and IIIA, for example, BeCl2, BF3
and AlCl3, whose Lewis formulas are shown:

ii. More than octet (central atom has excess of electrons):

Elements with an expanded valence (also called an expanded octet) have more than 8 electrons (often 10 or
12) in a Lewis structure. Elements in the third period and below, such as phosphorus, sulfur, and bromine,
often have an expanded valence because of their larger radii (when compared to the second-row elements)
and the availability of empty d orbitals in the valence shell.
For example PF5, SF6 and XeF4:

iii. Molecules containing an odd number of electrons:

Even if stable molecules of this kind (free radicals) are rare, they do exist. Free radicals can also be electron-
deficient compounds. Some examples are ClO2, NO and NO2 having 19, 11 and 17 valence electrons,
respectively.
For example, the best way to suggest the Lewis-like structure for the NO molecules is:

– –
Exercise: State the type of octet rule exception for: a. BH3 b. c. SeCl4 and d.
Properties of Covalent Compounds
Physical properties of covalent molecules depend heavily on the nature of their interaction with other
molecules (intermolecular forces).
Depending on the nature of these intermolecular interactions, covalent compounds have the following
properties.
a. At room temperature, most covalent compounds are gases or liquids.
b. Most covalent compounds have low melting and boiling points. Covalent compounds are volatile.
c. Most covalent compounds are poor conductors of electricity.Non-polar covalent compounds are non-
electrolytes because they do not conduct electricity. Generally covalent compounds exist as separate
molecules because electrically neutral atoms form them and the forces of attraction between these
molecules are relatively weak.
d. Most covalent compounds are soluble in non-polar solvents and are insoluble in polar solvents like
water.
e. Reactions of covalent compounds are slow compared to that of ionic compounds.
f. They have low density. The existence of a covalent compound in the liquid or gaseous state makes the
number of molecules per unit volume less, thereby leading to low density.
2.3.4 Molecular geometry
Molecular geometry is the three-dimensional arrangement of atoms in a molecule. The basis of this approach
is the assumption that electron pairs in the valence shell of an atom repel one another.
Valence Shell Electron Pair Repulsion (VSEPR) Theory
The basic principle of VSEPR theory is that the pair of valence-shell electron pairs around the central atom
arrange as far away from one another as possible to minimize electron-pair repulsions. The arrangements that
best minimize repulsions naturally depend on the number of electron sets.
In a polyatomic molecule, where there are two or more bonds between the central atom and the surrounding
atoms, the repulsion between electrons in different bonding pairs causes them to remain as far apart as
possible. Thus we can determine its specific shape from the number of atoms bonded to the central atom.
Electron Pair Arrangement and Molecular Shape
The electron pair arrangement is defined by the orientation/distribution of pairs of electrons, both bonding
and non-bonding (lone pair), around the central atom. On the other hand, the molecular shape is defined by
the relative positions of the atomic nuclei. Molecular shapes that occur when all the surrounding electrons are
bonding differ from molecular shapes when some of the electrons are non-bonding. Thus, the same electron
set arrangement can give rise to different molecular shapes.
For the prediction of geometrical shapes of molecules with the help of VSEPR theory, it is convenient to
divide molecules into two categories as molecules in which the central atom has no lone pair and molecules
in which the central atom has one or more lone pairs.
i. molecules in which the central atom has no lone pair
Consider molecules that contain atoms of only two elements, A and B, of which A is the central atom. These
molecules have the general formula ABx, where x is an integer 2, 3 ... (If x = 1, we have the diatomic
molecule AB, which is linear by definition.) In the vast majority of cases, x is between 2 and 6. In the
compounds of AB2, AB3, AB4, AB5 and AB6, the arrangements of electron pairs and the B atoms around
the central atom A are: linear, trigonal planar, tetrahedral, trigonal bi-pyramidal and octahedral, respectively.
Such arrangements can be seen in molecules such as BeCl2 (AB2), BF3 (AB3), CH4 (AB4) and PCl5 (AB5)
as shown below (Figure 2.7) by their ball and stick models.

Figure 2.7: The shapes of molecules in which the central atom has no lone pair
In the case of multiple (double or triple) bonds the counting is not different, because a double bond is
considered as one set and a triple bond as another set of electrons.
For example, in the case of CO2, O=C=O, there are two sets of electrons around the central atom, acetylene,
C2H2, H–C≡C–H, two sets of electrons around each of the central atoms.
ii. molecules in which the central atom has one or more lone pairs
In such molecules there are three types of repulsive forces—those between bonding pairs, those between lone
pairs, and those between a bonding pair and a lone pair. In general, according to the VSEPR model, the
repulsive forces decrease in the following order:
Lone pair vs. lone pair > lone pair vs. bonding pair > bonding pair vs. bonding pair
Why is that repulsions exerted by lone pair is greater than that of bonding pair?
Because they are localized closer to the central atom and they are not stabilized by attraction to multiple
nuclei. Thus increase their repulsive force. Bonding pairs, on the other hand are distributed more evenly
between two atoms, reducing their localized repulsive effect
The total number of bonding pairs and lone pairs, the molecules with lone pairs as ABxEy, where A is the
central atom, B is a surrounding atom, and E is a lone pair on A. Both x and y are integers; x = 2, 3. . , and y
= 1, 2 . . . Thus, the values of x and y indicate the number of surrounding atoms and number of lone pairs on
the central atom, respectively. The simplest such molecule would be a triatomic molecule with one lone pair
on the central atom and the formula is AB2E.
AB2E: Sulfur Dioxide (SO2)
The Lewis structure of sulfur dioxide is:

The SO2 molecule can be viewed as consisting of three electron pairs on the central S atom. Of these, two are
bonding pairs and one is a lone pair. Thus, the overall arrangement of three electron pairs is trigonal planar.
But because one of the electron pairs is a lone pair, the SO2molecule has a ―bent‖ shape.

Because the lone-pair versus bonding-pair repulsion is greater than the bonding-pair versus bonding-pair
repulsion, the two sulfur-to-oxygen bonds are pushed together slightly and the OSO angle is less than 120°.
AB3E: Ammonia (NH3)
The ammonia molecule contains of three bonding pairs and one lone pair:

The overall arrangement of four electron pairs is tetrahedral. But in NH3 one of the electron pairs is a lone
pair, so the geometry of NH3 is trigonal pyramidal. Because the lone pair repels the bonding pairs more
strongly, the three NH bonding pairs are pushed closer together:

AB2E2: Water (H2O)

A water molecule contains two bonding pairs and two lone pairs:

The overall arrangement of the four electron pairs in water is tetrahedral, the same as in ammonia.
However, unlike ammonia, the HOH angle is 104.5°. The geometry of H2O is bent.

AB4E: Sulfur Tetra fluoride (SF4)

The Lewis structure of SF4 is:
The central sulfur atom has five electron pairs whose arrangement is trigonal bi-pyramidal. In the SF4
molecule, however, one of the electron pairs is a lone pair, so the molecule must have one of the following
geometries:

In (a) the lone pair occupies an equatorial position, and in (b) it occupies an axial position. The axial position
has three neighboring pairs at 90° and one at 180°, while the equatorial position has two neighboring pairs at
90° and two more at 120°. The repulsion is smaller for (a), and indeed (a) is the structure observed
experimentally.

Guidelines for Applying VSEPR Model

Here are some guidelines for applying the VSEPR model:
1. Write the Lewis structure of the molecule, considering only the electron pairs around the central atom (that
is, the atom that is bonded to more than one other atom).
2. Count the number of electron pairs around the central atom (bonding pairs and lone pairs). Treat double
and triple bonds as though they were single bonds. If there is more than one central atom, treat each central
atom separately.
3. Use the VSEPR geometry to predict the shape of the molecule.
4. In predicting bond angles, note that a lone pair repels another lone pair or a bonding pair more strongly
than a bonding pair repels another bonding pair.
Molecular Shape and Molecular Polarity
Many aspects of molecule‘s chemical behavior can be understood if we know the geometry (shape) of a
substance. Molecular shape affects many properties of the molecule like molecular polarity, which in turn
influence melting and boiling points, solubility, and even reactivity.
Molecular polarity is created by molecules with a net imbalance of charge. In molecules with more than two
atoms, both shape and bond polarity determines the molecular polarity.
Bond Polarity and Dipole Moment
Polar and Non-Polar Covalent Molecules
Non-Polar bond results when the electrons are equally shared b/n the two atoms because their electro
negativities are the same or very similar. There is no charge separation, so no dipole moment is created.
Non- polar bonds often occur in molecules with identical atoms or symmetrical structures. E example O2

Polar covalent bond is a type of covalent bond in which the electrons are unequally shared between the two
atoms due to difference in electronegativity. This separation of charges create a dipole moment, making the
bond polar
The H–F bond is another example of a polar bond because fluorine is more electronegative than the hydrogen
atom. The bonding electrons spend more time near the fluorine atom than the hydrogen atom.

Polar covalent bonding occurs because one atom has a stronger affinity for electrons than the other. When
electrons are shared but shared unequally.
Dipole moment (µ): is measure of the separation of positive and negative charges in a molecule.
It is a vector sum of the bond moments in a molecule. Bond moment is a measure of polarity of a diatomic
covalent bond.
The dipole moment is given by µ
Where - the magnitude of the charge at either end, is the distance that separates the charge.
The SI-unit of dipole moment is coulomb-meter (C.m). Dipole moments are often expressed in the non-SI
unit Debye (D), where 1D = 3.33564 × 10–30 Cm.
A very polar molecule is one with a large dipole moment, while a non-polar molecule will have a zero-
dipole moment.
Note: For a diatomic molecule, the bond moment is the dipole moment. The dipole moment of a polyatomic
molecule (three or more atoms) depends on the geometry of the molecule. If the bond moments are equal in
magnitude but opposite in direction, then they will cancel each other and the resultant dipole moment will be
zero, provided that the vector sum of the bond moments is zero.
For a molecule made up of three or more atoms, both the polarity of the bonds and the molecular geometry
determine whether there is a dipole moment. Polar bonds do not necessarily lead to polar molecules. For
example, the large electronegativity difference between carbon and oxygen makes each C−O bond quite
polar. However, because carbon dioxide (CO2) has a linear shape, and its bonds are directed 180° from each
other, there is nonet dipole moment (μ); μ= 0 D.

Another molecule with identical atoms bonded to the central atom is water. Unlike carbon dioxide, water has
a significant dipole moment (μ= 1.87 D). In each O–H bond, electron density is pulled toward the more
electronegative O atom, but the bond polarities do not counter-balance each other, because the water
molecule is V-shaped. Instead, the bond polarities partially reinforce each other, and the oxygen end of the
molecule is considerably more negative than the other end.

Carbon dioxide and water demonstrate how molecular shape influences polarity.
When two or more different molecules have the same shape, the nature of the atoms surrounding the central
atom can have a major effect on the polarity of a molecule. Consider tetrachloromethane (CCl4) and
trichloromethane (CHCl3), two AB4 type molecules: tetrahedral shape with different polarities. In CCl4, the
surrounding atoms are all Cl atoms. Although each C–Cl bond is polar,the molecule is non-polar because the
individual bond polarities counter-balance each other. In CHCl3, an H atom substitutes for one of the Cl
atoms, disturbing the balance and giving chloroform a significant dipole moment.

If you consider the two constitutional isomers of dichloroethene (C2H2Cl2), they have the same molecular
formula. However, they have different physical and chemical properties. VSEPR theory predicts that all the
nuclei lie in the same plane with a trigonal planar molecular shape around each carbon atom.

The trans isomer has no dipole moment (μ= 0 D) because the C – Cl bond polarities balance each other. In
contrast, the cis-isomer is polar (μ= 1.89 D) because the bond dipoles partially reinforce each other, with the
molecular dipole pointing between the Cl atoms.
2.3.5 Intermolecular forces in covalent compounds
There are two types of electrostatic forces at work in any sample of matter.
i) Intramolecular force: is a force that exists within a particle (molecule)
 It affects the chemical property of the species.
ii) Intermolecular forces -are exists due to the attraction between ions and molecules.
 It affects the physical property of the species.
 Are relatively weak, because they exist between non-bonded atoms in adjacent molecules.
 Why does a polar liquid generally have a higher boiling point than a non-polar liquid of the same
molecular mass?
For any neutral molecule, there are three types of intermolecular forces.
Dipole-Dipole forces: When polar molecules are brought near one another, they give rise to dipole-dipole
forces
For compounds of approximately the same mass and size ,greater is the dipole moment, greater is the dipole-
dipole forces between their molecules, so greater is the energy required to separate their particles.
Example: Dipole-dipole forces give polar cis-1,2-dichloroethene a higher boiling point than nonpolar trans-1,
2-dichloroethene.
Hydrogen Bonding: is a special type of dipole-dipole forces that arise between molecules that have a
hydrogen atom bound to smaller sized, most electronegative atoms. These atoms are: Fluorine, Oxygen and
Nitrogen. The bond formed between hydrogen and such an atoms is highly polar.
The atom sequence that leads to an H bond (dotted line) is indicated below.

London Dispersion Forces (LDF)

 Dispersion forces are caused by a sudden shift of electron density in one side of the nucleus than the
other.
 Thus, non-polar molecules interact by inducing dipoles in each other leads to London Dispersion
Forces
 These forces are mainly responsible for the condensed state of non-polar substance like CO2, Cl2, and
noble gases
 It is the weakest intermolecular force due to temporary inducing dipoles.
 • For substances with the same molar mass the strength of the dispersion force is often influenced by
the molecular shape
• Shapes that allow more points of contact have more area over which electron clouds can be distorted,
so stronger attractions result.
• This is probably the reason why n-pentane (CH3CH2CH2CH2CH3) exhibits higher boiling point than
its isomer 2,2-dimethyl propane.

2.4 Metallic bonding

In simple terms, metallic bonding is referred to as bonding in metal atoms.
Metallic bonding: is the force of attraction which binds together the positive metal ions or Kernels with the
electrons within its sphere of influence.
It is also defined as interaction between metal nuclei and the delocalized electrons.
Metallic bonding can be imagined as sea of electrons in which positive metal ions are embedded.

In contrast to ionic bonding, the metal ions are not held in place as rigidly as in ionic solid. In contrast to
covalent bonding, no particular pair of metal atoms is bonded through any localized pair of electrons.
The valence electrons are shared among all the atoms in the substance, which is held together by the mutual
attraction of the metal cations for the mobile, highly delocalized electrons.
the extent of delocalization in metal is much greater. The bonding-electrons are free to move throughout the
three dimensional structure.
Properties of metals related to the concept of bonding
 Their atoms possess strong bonds
 Electrons can move freely in all directions in a metal. Thus they are good conductors of heat and
electricity
 Malleable: can be hammered into thin sheets
 Ductile: they can be drawn into wires
 Most metals are solids with high melting and much higher boiling points
2.5 Chemical bonding theories
Covalent bonds are more accurately explained using modern bonding theories: the valence bond
theory and the molecular orbital theory.
2.5.1 Valence Bond Theory
The basic principle of valence bond theory is that a covalent bond forms when orbitals of two atoms overlap
and the overlap region, which is between the nuclei, is occupied by a pair of electrons. By overlap, we mean
that the two orbitals share a common region in space.

For example, consider the formation of the H2 molecule from two hydrogen atoms. Each atom has the
electron configuration 1s1. As the H atoms approach each other, their 1s orbitals begin to overlap and a
covalent bond forms (Figure 2.9). Electron density is higher in the overlap region than anywhere else, and
the build-up of negative electron charge between the positive nuclei provides the electrostatic attraction that
holds the atoms together.

Figure 2.9: Atomic orbital overlap and bonding in H2

How is the strength of the bond between any two atoms affected by the extent of the overlap between the two
orbitals?
When two atoms are brought closely together, the repulsion of the atomic nuclei becomes more important
than the electron-nucleus attraction and the bond becomes unstable. There is a condition of optimal orbital
overlap that leads to maximum bond strength (bond energy) at a particular internuclear distance (bond
length).
The bond strength depends on the attraction of the nuclei for the shared electrons, so the greater the orbital
overlap, the stronger (more stable) the bond. The extent of overlap depends on the shapes and directions of
the orbitals. An s orbital is spherical, but p and d orbitals have more electron density in one direction than in
another. Thus, whenever possible, a bond involving p or d orbitals will be oriented in the direction that
maximizes overlap.
In the HF bond, for example, the 1s orbital of H overlaps the half-filled 2p orbital of F along the long axis of
that orbital (Figure 2.10). Any other direction would result in less overlap and, thus, a weaker bond.
Note that a single bond consists of two electrons of opposite spin: hence, the two atomic orbitals that give
rise to a single bond can have no more than two electrons in total.

Figure 2.10: Orbital and spin pairing in the formation of a HF molecule

Similarly, in the F–F bond of F2, the two 2p orbitals interacts end-to-end, that is along the orbital axes, to
attain maximum overlap (Figure 2.11).

Figure 2.11: Orbital and spin pairing in the formation of a F2 molecule

When two atomic orbitals overlap to build up electron density along the two axis between the two nuclei, the
resulting localized bond is called a sigma bond (σ). Such an overlap is sometimes referred to as a head on,
end-to-end, end on or linear overlap. In Figures 2.9, 2.10 and 2.11, head-to-head overlap resulted in sigma
bonds.
Exercise: Identify the overlapping orbitals that form the single bond in a BrCl molecule.
Solution: 4p orbital of Br and 3p orbital of Cl interacted end-to-end that is along the orbital axes, to attain
maximum overlap.
So far we have considered only sigma bonds, bonds in which the highest electron density lies along the
bond axis (an imaginary line joining the nuclei) in between the bonded nuclei. The shape of p atomic orbitals
allows them to overlap not only in a head-to-head fashion. If they are oriented in a parallel position, they can
overlap sideways or laterally as shown in Figure 2.12. A bond formed in this way is called pi-bond (π).
Figure 2.12: Formation of a pi bond (π bond) by the overlap of two half-filled p orbitals that are
perpendicular to the internuclear axis
Note that the directional nature of p orbital allows to overlap in two ways: end-to-end or sideways. These two
modes give rise to the two types of covalent bond: sigma (σ) and pi (π) bond, respectively. However, s-s
and s-p will always overlap along the nuclear axis, resulting only in sigma bonds. Pi bonds are present in
molecules containing multiple bonds.
Exercise: Can you give examples of compounds contain multiple bonds? CH2CH2, C2H2
All of the electron density in a π bond is found in lobes above and below the line connecting the atomic
centers: one above and one below the sigma bond axis. One π bond holds two electrons that occupy both
regions of the bond. A double bond always consists of one σ and one π bond. The double bond increases
electron density between the nuclei. A triple bond consists of one σ and two π bonds.
Exercise:
1. Which bond is stronger: sigma (σ) or pi (π)? Why?
π is the strongest b/c more electron density(more stability) is resulted than sigma bond
2. Compare the bond strength and length of single, double, and triple bonds.
Bond strength: triple bonds > double bonds > single bonds
Bond length: single bonds > double bonds > triple bonds
Hybridization of Orbitals
Hybridization
 The combination of atomic orbital is called hybridization
 The word ‗hybridization‘ means ‗mixing
 Hybrid orbitals may be formed by mixing the characters of atomic orbitals that are close in energy
 The number of bond formed by an atom is the same as the number of unpaired electron that
combined in ground state.

Consider covalent bond formation of carbon atom. From its ground state configuration, two unpaired
electrons in the 2p subshell are observed.
One can predict the simplest hydrocarbon molecule to be CH2, by overlapping thetwo unpaired electrons
from two H atoms with the two unpaired electrons of carbon. However, experiment shows that CH2 is not a
stable molecule. The simplest stable hydrocarbon is methane, CH4. To account for this, one of the 2s
electrons is promoted to the empty 2p orbital. To excite the 2s electron to a higher energy sublevel, energy
must be absorbed. The resulting electron configuration is that of an excited state having energy greater than
the configuration in the ground state.

Valence bond theory proposes that the one 2s and all three 2p orbitals of the carbon atom mix to produce
four new orbitals ( sp3 ) that are equivalent to each other in energy and in shape and pointing in different
directions with equal H–C–H bond angles.
This blending is called hybridization and the resultant orbital as hybrid orbitals. The symbols used for hybrid
orbitals identify the kinds and numbers of atomic orbitals used to form the hybrids.
The number of new hybrid orbitals is equal to the total number of atomic orbitals that are combined.
sp hybrid orbital
Combination (mixing) of one s and one p orbital is called sp hybridization and the resultant orbitals are
called sp hybrid orbitals. sp type of hybridization involves the mixing of one s and one p orbital resulting in
the formation of two equivalent sp hybrid orbitals. Each sp hybrid orbitals has 50% s-character and 50% p-
character.
VB theory explains this by proposing that mixing two non-equivalent orbitals of a central atom one s and one
p, gives rise to two equivalent sp hybrid orbitals that lie 180° apart.
Example: In the triatomic molecule BeCl2 the 2s and one of the 2p orbitals of the Be atom are hybridized into
sp hybrid orbitals. The remaining two 2p orbitals are left un-hybridized and unoccupied in the orbital
diagram.
Figure 2.13: Excitation of Be 2s electrons and sp hybrid orbitals formation

Figure 2.14: The formation of two equivalent sp hybrid orbitals in Be

These two sp hybrid orbitals face opposite directions, forming an angle of 180°. Each of the sp hybridized
orbitals overlaps with the 2p-orbital of chlorine axially and forms two BeCl sigma bonds. This is shown in
Figure 2.15.

Figure 2.15: The sp hybrid orbitals in gaseous BeCl2 sp2 hybrid orbitals

sp2 hybrid orbitals

In this hybridization there is involvement of one s and two p-orbitals in order to form three equivalent sp2
hybridized orbitals. For example, in BCl3 molecule, the ground state electronic configuration of central
boron atom is 1s22s22p1.
In the excited state, one of the 2s electrons is promoted to vacant 2p orbital (Figure 2.16) as a result boron
has three unpaired electrons. These three orbitals (one 2s and two 2p) hybridize to form three sp2 hybrid
orbitals as shown in Figure 2.16.

Figure 2.16: Excitation of boron 2s electrons and sp2 hybrid orbitals formation
The three equivalent hybrid orbitals formed are oriented in a trigonal planar arrangement and overlap with 2p
orbitals of chlorine to form three B-Cl bonds. Therefore, in BCl3 (Figure 2.17), the geometry is trigonal
planar with ClBCl bond angle of 120°.
Figure 2.17: sp2 hybrid orbitals and bonding in BCl3
What is the percent of s-character and p-character in each sp2 hybrid orbital?
sp3 hybridization
Carbon, the central atom in a molecule of methane CH4 has only two unpaired electrons in the ground state
rule. Carbon in its excited state can form four bonds. The one 2s and three 2p-orbitals of carbon are mixed to
produce four new orbitals that are equivalent to each other in energy and in shape, but pointing in different
directions,

Figure 2.18: Excitation of carbon 2s electrons and sp3 hybrid orbitals formation

Figure 2.19: sp3 hybrid orbitals and bonding in methane

The structure of NH3 and H2O molecules can also be explained with the help of sp3 hybridization. In NH3,
the valence shell (outer) electronic configuration of nitrogen in the ground state is 2s22px12py12pz1. In the
formation of NH3, one 2s orbital and three 2p orbitals of nitrogen are mix up forming four hybrid orbitals
(sp3) of equivalent energy. One of the sp3 hybrid orbitals has a lone pair of electrons and the other three sp3
orbitals are half-filled.
These three half-filled hybrid orbitals overlap with 1s orbitals of hydrogen atoms to form three N–H sigma

repulsion between two bond pairs of electrons. So the molecule gets distorted and the bond angle is reduced
to 107° from 109.5°. The geometry of such a molecule will be pyramidal as shown in Figure 2.20.

Figure 2.20: sp3 hybrid orbitals and bonding in NH3

In the case of H2O molecule, the four oxygen orbitals (one 2s and three 2p) undergo sp3 hybridization
forming four sp3 hybrid orbitals out of which two contain one electron each and the other two contain a pair
of electrons. These four sp3 hybrid orbitals acquire a tetrahedral geometry, with two corners occupied by
hydrogen atoms while the other two by the lone pairs. The bond angle in this case is reduced to 104.5° from
109.5° (Figure 2.21) and the molecule thus acquires a V-shape or angular geometry.

Figure 2.21: sp3 hybrid orbitals and bonding in H2O

Why is the HOH bond angle in water less than the HNH bond angle in NH3?
Hybridization of elements involving d orbitals
The elements present in the third period contain d orbitals in addition to s and p orbitals. The energy of the
3d orbitals is comparable to the energy of the 3s and 3p orbitals. The energy of 3d orbitals is also comparable
to those of 4s and 4p orbitals.
As a consequence, the hybridization involving either 3s, 3p and 3d or 3d, 4s and 4p is possible.
sp3d hybridization
PCl5, the central atom phosphorus has only three unpaired electrons in its ground state. Electrons must be
unpaired to provide the correct number of unpaired electrons for bond formation

Figure 2.22 (a): sp3d hybrid orbitals filled by electron pairs donated by five Cl atoms
Now the five orbitals (i.e., one s, three p and one d orbitals) are available for hybridization to yield a set of
five sp3d hybrid orbitals which are directed towards the five corners of a trigonal bi-pyramidal as in Figure
2.22b.

Figure 2.22 (b): Trigonal bipyramidal geometry of PCl5 molecule

Note that all the bond angles in trigonal bi-pyramidal geometry are not equivalent. In PCl5 the five sp3d
orbitals of phosphorus overlap with the singly occupied p orbitals of chlorine atoms to form five P–Cl sigma
bonds. Three P–Cl bonds lie in one plane and make an angle of 120° with each other; these bonds are termed
as equatorial bonds. The remaining two P–Cl bonds–one lying above and the other lying below the equatorial
plane, make an angle of 90° with the plane. These bonds are called axial bonds. As the axial bond pairs suffer
more repulsive interaction from the equatorial bond pairs, axial bonds have been found to be slightly longer
and hence slightly weaker than the equatorial bonds; which makes PCl5 molecule more reactive.
Sp3d2 Hybridization
Another structure featuring an expanded octet is SF6. Here, six hybrid orbitals are required in order to
describe bonding
SF6 molecule has a regular octahedral geometry as shown in Figure 2.23b.
Figure 2.23 ( a ): sp3d2 hybridization

Figure 2.23 (b): Octahedral geometry of SF6 molecule

Multiple bonds and hybridization
We will discuss here the ethene, C2H4, and acetylene, C2H2 molecules; however pi bonds are also present in
other molecules such as N2, SO2, NO3, etc.
Ethylene

Figure 2.25: Bond formation in the ethene molecule, C2H4: (a) five σ bonds and (b) one π bond
All the C–H bonds in C2H4 are formed by the overlap of sp2 hybrid orbitals of the C atoms with 1s orbitals of
the H atom, A double covalent bond consists of one σ and one π bond.
Generally:
Example:

Exercise:
Discuss the bonding in ammonium and sulphate ions: predict the ideal bond angles, bond length, shape of the
ions, and the number of σ and π bonds.
2.5.2 Molecular orbital theory(MOT)
 In MOT, the bonding between atoms is described as a combination of their atomic orbitals.
  The electrons are delocalized since they are not assigned to a particular atom or bond.
 MOT allows one to predict the distribution of electrons in a molecule which in turn can help to
predict molecular properties such as shape, magnetism, and Bond Order.
Bonding and Anti-bonding Molecular Orbitals (MOs)
 BMO– MOs with electron density concentrated in the regions between atoms.
 Bonding MOs have lower energy and greater stability than the atomic orbitals from which it was
formed.
 Anti-bonding Molecular Orbital – MOs with electron density concentrated in regions other than
between the atoms.
 Anti-bonding MOs have higher energy and lower stability than the atomic orbitals from which it was
formed.

 Similar to the VBT, the types of bonds in MOT can be sigma or pi bonds. In the pi bonding, there are
an overlap of atomic orbitals in between py-py and pz-pz orbitals to form π2py, π2pz bonding and π*2py,
π*2pz anti-bonding molecular orbitals.
 The number of molecular orbitals = the number of atomic orbitals combined
Determining Bond Order
 Bond Order indicates the strength of the bond, the higher the Bond Order the stronger the bond.
 Bond order determines the stability of the molecule. In general, the higher the bond order, the
stronger the bond.
 Bond order can be calculated as follows:

Bond order Type of bond and stability Example

0 No bond & not stable, He
2
 1 Single bond, stable H
2

2 Double bond, more stable O

2

3 Triple bond, very stable N

2

N.B MOT can more accurately describe partial bonds (for example in H2+, where the Bond Order =1/2)

MO Energy level Diagram

Examples:
He2:
Molecular orbital configuration for He2: (1s)2(*1s)2,
Bond order for He2: BO = ½ (2 – 2) = 0, Therefore, He2 does not exist.

Lithium (Li2):
Molecular orbital configuration for Li2: (1s)2(*1s)2(2s)2,
Bond order for Li2: BO = ½ (4 – 2) = 1, Therefore the bond between Li–Li is single bond.
Nitrogen (N2), Electron Configuration for N atom is: 1s2, 2s2, 2p3
Electrons found in N2: N + N = 7 + 7 = 14
MO configuration for N2: (s1s)2(s*1s)2(s2s)2(s*2s)2(p2p)4(s2p)2
Bond order for N2: BO = ½ (10 – 4) = 3
Triple bond is formed b/n N-N atoms (NN).

Exercise: Use the MO theory to predict the bond order and the number of unpaired electrons in O22–, O2–,
O2+, NO and CO.
Magnetic and diamagnetic Properties
Molecules with unpaired electrons exhibit paramagnetic properties. The species is attracted by an external
magnetic field. When all the electrons are paired, there is diamagnetism. Such species are not attracted (and,
in fact, are slightly repelled) by a magnetic field.
2.6 Types of Crystals
A crystal is a piece of a solid substance that has plane surface, sharp edges, and a regular geometric shape
A structural unit of a crystalline solid has a characteristic repetitive pattern
There are four important classes of crystalline solids.