PHYSICAL CHEMISTRY

Matter and its properties

Bohr’s planetary theory

Bohr’s planetary theory explained the structure of an atom and the behaviour of
electrons.
According to this theory, electrons orbit the nucleus in a fixed, circular orbits at
specific energy levels, like the planets in the solar system. These energy levels were
quantized, meaning electrons could only occupy specific energy states and could
only transition between those levels by either absorbing or emitting a discrete
amount of energy in the form of a photon. This theory also introduced the concept of
ground state, where the electron orbits the nucleus at its lowest energy level, excited
states, where the electron absorbs energy and jumps to higher energy levels.
Bohr’s theory provided a foundation for modern atomic theory and led to further
development in the understanding of quantum mechanics

Main postulates of Bohr’s planetary theory

Bohr’s planetary theory of the atom was based on the following postulates:
1. Electrons move around the nucleus of an atom in fixed, circular orbits.
2. The electrons can exist only in certain allowed orbits, which correspond to
specific energy levels.
3. While an electron is in a particular energy level, it does not radiate energy.
This energy is only emitted when the electron jumps from one energy level to
another.
4. The energy of the emitted radiation corresponds to the difference in energy
between the initial and the final energy levels.
5. The size of the orbit and the energy of the electron are related. Electrons in
larger orbits have more energy than those in smaller orbits.
6. Electrons can only make transitions between energy levels that correspond to
a specific amount of energy, known as a quantum. These transitions produce
or absorb photons that have a frequency proportional to difference in energy.
These postulates provided a framework for understanding the behaviour of electrons
within atoms.
The diagrams below show Bohr's model of the atom.

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Continuous and line spectra

1. Continuous spectrum
A continuous spectrum is a spectrum of electromagnetic radiation containing
photons of all energy levels within a specific range. Unlike atomic spectra, which
consists of only specific energy levels, a continuous spectrum contains a radiation of
all energies resulting in a smooth display of colours or wavelengths.
Examples of sources of continuous spectra include a hot solid object, such as a light
bulb filament, a glowing gas or plasma.
Continuous spectra are important in both astronomy and laboratory experiments, as
they can be used to help identify the composition and temperature of objects emitting
radiation.
2. Line spectrum
A line spectrum is a spectrum produced by an excited atom or molecule that
contains only discrete wavelengths or colours of electromagnetic radiation. These
wavelengths correspond to specific energy level transitions within the atom or
molecule.

Differences between continuous spectrum and line spectrum

There are several differences between continuous spectrum and line spectrum.
These are:
1. Definition:
A continuous spectrum contains radiation of all energies within a certain range,
whereas a line spectrum contains only specific wavelengths of radiation.
2. Source :
A continuous spectrum is emitted by a hot, dense object such as a light bulb filament
or a star, whereas a line spectrum is produced when an excited atom or molecule
emits light.
3. Appearance:
A continuous spectrum appears as a smooth display of colours or wavelengths while
a line spectrum appears as a series of discrete lines or bands.
4. Composition:
A continuous spectrum contains radiation of all energies, while a line spectrum
contains only specific energies that correspond to the energy level transitions of the
emitting atom or molecule.
5. Usage:

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Continuous spectra are used to identify the temperature and composition of a source
emitting light while line spectra are used to identify the chemical composition of a
source emitting light.
6. Examples:
Examples of sources for continuous spectra include the sun, light bulbs, and
blackbody radiators, while the line spectra are typically emitted by excited atoms or
molecules, such as hydrogen, helium or neon.

Relationship of the lines in the emission spectrum of hydrogen to electron

energy levels
The lines in the emission spectrum of the hydrogen are directly related to the energy
levels of the hydrogen atom. When an electron in a hydrogen atom is excited, it
moves from the ground state (lowest energy level) to a higher energy level. This
higher energy is not stable, and the electron will eventually return to its ground state
by releasing energy in the form of a photon of light.
The energy of this photon is directly proportional to the difference between the higher
and lower energy levels of the electron. Since each energy level of the electron in a
hydrogen atom is fixed, the energy of the released photon is also fixed and
corresponds to specific wavelength or colour of light. Therefore, each emission line
in the hydrogen spectrum corresponds to a specific energy level transition for the
electron in the hydrogen atom.
The lines in the spectrum represent the different energy levels that the electron can
occupy and the corresponding wavelengths of the photons emitted as the electron
transitions back to a lower energy level.
The diagrams below show the relationship between the line spectrum of hydrogen
and energy levels.

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Contribution of Quantum theory towards the development of the atomic
structure
Quantum theory has made significant contributions toward the development of the
atomic structure. Some of these contributions are:
1. Wave-particle duality:
Quantum theory introduced the concept of wave-particle duality, which suggests that
particles could exhibit both wave-like and particle-like behaviour. This theory helped
scientists to understand the behaviour of electrons in atoms, as electrons exhibit
wave-like behaviour in their movement around the nucleus.
2. Discrete energy levels:
Quantum theory introduced the concept of energy levels in atoms. This means that
electrons can only exist at certain energy levels around the nucleus and cannot exist
anywhere in between.
3. Uncertainty principle:
Quantum theory introduced the uncertainty principles, which states that it is
impossible to know both the position and the momentum of an electron at the same
time. This principle helped scientists understand why electrons exist in certain
energy levels and not in between them.
4. Quantum numbers:
Quantum theory introduced the concept of quantum numbers which describe the
energy levels and positions of electrons in atoms. These quantum numbers help
predict the properties of atoms and their behaviour during chemical reactions.
5. Electron spin:
Quantum theory also introduced the concept of electron spin, which explains why
two electrons in the same electron orbital have opposite spins. This concept helps
scientists understand the behaviour of electrons in atoms and their contribution to
the magnetic properties of materials.
These concepts introduced by quantum theory have helped scientists understand
the fundamental behaviour of electrons and predict their properties and behaviour
during chemical reactions.

An orbit and an orbital

1. An orbit
An orbit refers to the path that an object, such as a planet or an electron, takes when
it revolves around another object under gravitational influence. In the context of
atomic structure, an electron orbit is the path taken by an electron as it moves
around the nucleus of an atom. The movement of the electron around the nucleus is
determined by its energy level, which represents the electron’s potential energy at a
given distance from the nucleus.
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 2. An orbital
In atomic theory, an orbital is a region of space around the nucleus of an atom,
where an electron is most likely to be found. An orbital is characterized by a set of
quantum numbers that describe its size, shape, and orientation in space. Unlike
orbits, orbitals do not describe the exact path of the electron around the nucleus but
rather describe the probability of finding an electron in a particular region of space.
There are four quantum numbers that describe the electron orbital in an atom:
(a) Principal quantum number(n):
The principal quantum number determines the energy level or shell of an electron.
The larger the value of n, the higher the energy level and the farther the orbital is
from the nucleus.
(b) Angular momentum quantum number/Azimuthal quantum number(l):
The angular momentum quantum number determines the shape of the orbital. The
values of l range from 0 to (n -1), and each value corresponds to a particular shape
of the orbital.
(c) Magnetic quantum number(m):
The magnetic quantum number determines the orientation of the orbital in space.
The values of m range from (-l) to (+1), and each value corresponds to a particular
spatial orientation of the orbital.
(d) Spin quantum number(s):
The spin quantum number determines the direction of the electron’s spin. Electrons
can only have one of two spin states, either spin-up/clockwise(+½) or
spin-down/anticlockwise(-½).

Differences between an orbit and an orbital

An orbit and an orbital are both used to describe the location of an electron in an
atom, but they have some significant differences:
1. Definition:
An orbit refers to the path that an electron takes as it revolves around the nucleus of
an atom. On the other hand, an orbital refers to a region of space around the nucleus
where an electron is likely to be found.
2. Limitations:
Obits were originally thought to be well defined paths that electrons follow around the
nucleus, similar to the way the planets orbit around the sun. However, this idea was
discarded in the quantum mechanical model of the atom, where behaviour is instead
described using orbitals. The concept of orbitals allows for a more accurate
description of the electron’s location and behaviour in an atom compared to orbitals.
3. Energy:
Orbits are defined by a specific energy level, while orbitals are associated with a
range of energy levels.

Quantum numbers
Quantum numbers are integers or half-integers that describe the properties of
electrons in an atom. There are four types of quantum numbers-principal quantum
number, azimuthal quantum number, magnetic quantum number and spin quantum
number.
Here is a brief explanation of each quantum number.
1. Principal quantum number(n):
This quantum number determines the energy level of an electron and describes the
size of the electron cloud. It can have any positive value starting from 1.

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And when the electron occupies the higher energy level, this is described as in the
excited state.
Shell K L M N O
Orbital s s, p s, p, d s, p, d, f s, p, d, f, g

2. Azimuthal quantum number or Angular Momentum (l )

This quantum number indicates the shape of the electron cloud or the subshell in
which an electron is present. It can have values from 0 to (n-1).
Angular momentum number must not be negative.
For instance, when n=1, l is 0 and this refers to an s-orbital; when n = 2, l = 0, 1 and
this refers to a p-orbital; when n = 3, l =0, 1, 2 and this refers to a d-orbital; l=3
implies an f-orbital. An electron with n = 2 and l = 0 will be a 2s electron.
Principal quantum Angular Momentum or
number, n Azimuthal Quantum Number
(l ) = n-1
1 O ie s –orbital
2 0,1 ie p –orbital
3 0,1,2 ie d –orbital
4 0,1,2,3 ie f –orbital

3. Magnetic quantum number(m):

This quantum number specifies the orientation of the electron cloud in space. It can
have values from (-l) to (+l).

It is sometimes called the orbital-orientation quantum number.

For a given value of l, ml takes the values of −l ≤ml ≤+ l. For example, if l =1, ml = -1,
0, +1 and this refers to the p-orbital which has 3 degenerate orbitals. For l = 2, ml = -
2, -1, 0, +1, +2 referring to a d-orbital with 5 degenerate orbitals. For l =0, ml =0 and
this refers as to an s-orbital; l = 1 is p-orbital, l =2 is d-orbital and l =3 is f-orbital.
The values of an orbital of magnetic quantum number are set by the angular
momentum quantum number that is, l determines ml .

Principal Angular Momentum Magnetic quantum Number of

quantum or Azimuthal number, degenerate orbitals
number, n Quantum Number - l < ml <=+l
(l ) = n-1
1 0 ml = 0 ie s-orbital 1 ie s-orbital
2 0,1 ml = -1,0,1 ie p- 3 ie px, py and pz
orbital orbitals
3 0,1,2 ml = -2, -1, 0,+1,+2 5 ie d1,d2,d3,d4 and
ie d-orbital d5 orbitals
4 0,1,2,3 ml = -3, -2, -1, 7 ie f1,f2,f3,f4, f5, f6
0,+1,+2,+3 ie f- and f7 orbitals
orbital
NB:
The s-orbital have no suborbital / degenerate orbitals ie s-orbital
The p-orbital have 3 suborbital / degenerate orbitals ie px, py and pz orbitals
The d-orbital have 5 suborbital / degenerate orbitals ie d1,d2,d3,d4 and d5 orbitals
The f-orbital have 7 suborbital / degenerate orbitals ie f1,f2,f3,f4, f5, f6 and f7 orbitals

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 4. Spin quantum number(s):
This quantum number describes the spin of an electron, which is a fundamental
property of all particles. It can be either (+½) or (-½).
These quantum numbers play a crucial role in determining the electron configuration
of an atom and understanding its behaviour. They also help us in predicting the
position of electrons in an atom by providing a framework for describing energy
states and orbitals.

For example, the set of quantum numbers for the lone electron is hydrogen (Z=1) is
+1
n = 1, l ±0 . By convention is assigned to the first electron in an orbital.
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All orbitals are designated by nl x, where n is the main level, l is orbital and x is the
number of electrons.

The importance of quantum numbers to the electron structure of the atom

Quantum numbers play an important role in understanding the electron structure of
an atom. The electron structure refers to the arrangement of electrons in an atom’s
different energy levels and subshells.
Here are some reasons why quantum numbers are important in this regard:
1. Describing the electron energy levels:
The principal quantum number(n) allows us to determine the energy levels available
to electrons in an atom. Each energy level corresponds to an electron shell, and the
value of n determines the number of subshells and electrons that can reside in each
shell.
2. Specifying the subshells:
The azimuthal quantum number (l) provides information about the subshells within
each shell. It determines the shape of the subshell and its orientation in space. This
helps us to predict the electron distribution more accurately.
3. Determining the electron orientation:
The magnetic quantum number(m), indicates the orientation of the electron cloud in
space relative to a magnetic field. It helps us to understand spatial arrangement of
electrons within subshells.
4. Predicting electron spin:
The spin quantum number(s), describes the spin of each electron, which is important
for understanding the electron configuration of an atom. Two electrons with opposite
spins can occupy the same orbital, which has important consequences for the
chemical and physical properties of different elements.

Examples of orbits and orbitals

An orbit is described by a set of quantum numbers. Here are a few examples of
orbits.
1. The first orbit (n=1) is the closest to the nucleus and can hold up to two
electrons.
2. The second orbit (n=2) is farther away from the nucleus and can hold up to
eight electrons, arranged in two subshells (s and p).
3. The third orbit (n =3) is even farther away from the nucleus and can hold up to
18 electrons, arranged in three subshells (s, p and d).
An orbital is defined by a set of quantum numbers (n,l,m). Here are a few examples
of orbitals:
1. The s orbital is the lowest orbital, with a spherical shape and can hold up to
two electrons. The s orbital is shown below.

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 2. The p orbit p y ,❑and p z ), have a dumb-bell shape and can hold up to six
electrons (two in each orbital). These orbitals are found in the second and
higher energy levels. The p orbitals are shown below.

Shape of p- orbital

3. The d orbitals have more complex shapes called cloverleaf and can hold up
to ten electrons. These orbitals are found in the third energy level and higher.

Rules for filling electrons in quantum numbers.

Aufbau’s principle
Aufbau’s principle, also known as the building-up principle, is a fundamental principle
in chemistry stating that the atomic orbitals are filled with electrons in order of
increasing energy. Specifically, electrons will fill lower energy atomic orbitals
before moving on to higher energy levels. This principle is used to determine the
electron configuration of atoms and the order in which the orbitals are filled.

Pauli’s exclusion principle

Pauli’s exclusion principle is a fundamental principle in quantum mechanics that
states that no two electrons in an atom can have the same set of quantum
numbers. In other words, if two electrons are in the same orbital, they must
have opposite spins. The principle is essential in determining the structure of
atoms, as it limits the number of electrons that can occupy each orbital and
organizes the electron configuration of atoms in the periodic table.

Hund’s rule of maximum multiplicity

Hund’s rule of maximum multiplicity is a principle in quantum mechanics that states
that within a subshell, electrons will occupy orbitals singly, with their spins
parallel’ before they pair up with opposite spins.
In other words, if two or more orbitals having the same amount of energy are
unoccupied, then electrons will start occupying them singly, before they fill
them in pairs.

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This means that electron pairing in p and d orbitals cannot occur until each orbital of
a given subshell contains one electron or is singly occupied.
This rule is based on the fact that electrons in orbitals with parallel spins repel each
other less than electrons with opposite spins, leading to a lower potential energy for
the system. Therefore, when electrons occupy a subshell, they will make the most
energetic configuration by occupying orbitals singly before pairing up.
This rule is important in determining the electron configuration of atoms.

How to express electron configuration using s, p, d notation

To express the electron configuration of an atom using s, p, d notation, you first need
to identify the principal quantum number of the highest energy level occupied by
electrons, which is equal to the period number of the element in the periodic table.
Then you assign the electrons to each subshell in the following order:
1. First, the 1s orbital is filled before any other orbital.
2. Next, the 2s orbital is filled before the 2p orbital starts to fill.
3. Then, the 3s orbital is filled before the 3p orbital starts to fill.
4. After that, the 4s orbital is filled before the 3d orbital begins to fill.
That is, 1s2s2p3s3p4s3d.
So, for example, the electron configuration of Carbon(C), which has 6 electrons, can
be expressed in s, p, d notation as follows:
2 2 2❑
1s 2s 2 p .
This indicates that the first energy level (n = 1) is filled with two electrons in the 1s
orbital, while the second energy level (n = 2) is filled with four electrons in the 2s and
2p orbitals , with two electrons in each.

How to express electron configuration using ‘ electrons-in-boxes’ method

The electron configuration of an atom can also be expressed using the ‘electrons-in-
boxes’ method.
In this method, each orbital is represented as a box , and the electrons are
represented by arrows, with the direction indicating their spin.
For example, the electron configuration of carbon (C ) with 6 electrons can be
represented as follows:
1s
↑↓
2s
↑↓

2p
↑ ↑
In this representation, the first energy level (n= 1) has only one orbital, the 1s orbital,
with electrons represented by a pair of arrows pointing up and down. The second
energy level (n=2) contains two orbitals: the 2s orbital, which has two electrons
represented by arrows pointing up and down, and the 2p orbital, which has two
electrons.
Differences in stability between fully filled, half-filled and partially filled orbitals
The stability of an atom depends on the electron configuration of its orbitals.
A fully filled or half-filled orbital is more stable than a partially filled orbital due to the
following reasons:
1. Exchange energy:
Fully filled and half-filled orbitals have lower exchange energy compared to partially
filled orbitals. Exchange energy is the energy required by two electrons to occupy the
same orbital. In fully filled or half-filled orbitals, there is no need for electrons to
occupy the same orbital, hence exchange energy is minimized.

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 2. Repulsion energy:
Partially filled orbitals have more repulsion than fully filled or half-filled orbitals.
Repulsion energy is the energy required for electrons to avoid each other due to their
negative charge. In partially filled orbitals, electrons are more closely packed, and
hence repulsion energy is maximized.
3. Stability of subshells:
Fully filled and half-filled subshells are more stable than partially filled subshells. This
is due to the fact that fully filled and half-filled subshells have less energy than
partially filled subshells.

The electrons move around the nucleus in orbits which

correspond to specific energy levels.
An orbital is a region of space around the nucleus of an
atom, where an electron is mostly likely to be found.
The electron orbital is described by four quantum
numbers: principal quantum number, azimuthal quantum
number, magnetic quantum number and spin quantum
number.

Electron configuration is the arrangement of electrons in

the orbitals of an atom.
The electron configuration of atoms is governed by three
rules/principles. These are Aufbau’s principle, Pauli’s
exclusion principle, and Hund’s rule of maximum multiplicity.
Electrons are filled into the orbitals using the

Condensed Electronic Configuration

The following are the electronic configuration of the 1st 30 elements.
Elem 1s 2s 2px 2py 2pz 3s 3px 3py 3pz 4s Representation
ent
1H ↿ 1s1
2He ↿⇂ 1s2
3Li ↿⇂ ↿ 1s2 2s1
4Be ↿⇂ ↿⇂ 1s2 2s2
5B ↿⇂ ↿⇂ ↿ 1s2 2s2 2px1
6C ↿⇂ ↿⇂ ↿ ↿ 1s2 2s2 2px12py1
7N ↿⇂ ↿⇂ ↿ ↿ ↿ 1s2 2s2 2px12py12pz1
8O ↿⇂ ↿⇂ ↿⇂ ↿ ↿ 1s2 2s2 2px22py12pz1
9F ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ 1s2 2s2 2px22py22pz1
10Ne ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ 1s2 2s2 2px22py22pz2
11Na ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ 1s2 2s2 2px22py22pz2 3s1
12Mg ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ 1s2 2s2 2px22py22pz2 3s2
13Al ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ 1s2 2s2 2px22py22pz2 3s2 3px1
14Si ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ ↿ 1s2 2s2 2px22py22pz2 3s2
3px13py1
15P ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ ↿ ↿ 1s2 2s2 2px22py22pz2 3s2
3px13py1 3pz1
16S ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ ↿ 1s2 2s2 2px22py22pz2 3s2
3px23py1 3pz1
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 Cl
17 ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ 1s2 2s2 2px22py22pz2 3s2
3px23py2 3pz1
Ar
18 ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ 1s2 2s2 2px22py22pz2 3s2
3px23py2 3pz2
K
19 ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ ⇂ ↿ ⇂ ↿ ⇂ ↿ 1s2 2s2 2px22py22pz2 3s2
3px23py2 3pz2 4s1
Ca
20 ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿ ⇂ ↿ ⇂ ↿ ⇂ ↿ ⇂ 1s2 2s2 2px22py22pz2 3s2
3px23py2 3pz24s2

For convenience condensed electronic configuration is used to simplify electronic

configuration presentation. The K-shell can be represented by helium core 2[He] =
1s2. The L-shell can be represented by the neon core 10[Ne] = 1s2 2s2 2px2 2py2 2pz2.
The N-shell can be represented by argon core 18[Ar] = 1s2 2s2 2px2 2py2 2pz2 3s2 3px2
3py2 3pz2. Example; 19K = 10[Ne] 3s2 3px2 3py2 3pz2 4s1, 20Ca = 10[Ne] 3s2 3px2 3py2 3pz2
4s2.
After calcium (Ca), the next elements, scandium (Sc) to zinc (Zn) have their
electrons entering into the 3d-orbital. These elements are known as the first
transition series.

The configurations of 24Cr (B) and 29Cu (B) are very stable than that of its A
counterparts.
This is because there is high stability associated with half-filled outer
degenerate orbitals and fully filled orbitals than partially filled orbitals.

Level 2:
• How did Bohr answer the objection that an electron traveling in a circular
orbit would not radiate energy and fall into the nucleus?

Level 3:
Differentiate between the following:
a) Line and continuous spectra
b) Orbit and orbital

Level 4:
Describe emission spectrum of gaseous hydrogen atoms and construct an
explanation of how it is related to the energy levels in the atom

Level 3:
Copy and complete the table below:
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 notatio
n l n

1 0

2 0

3 0

Level 3:
Copy and complete the table below:

Su Maxi Num
bs mum ber
hel numb of
l er of orbit
electr als
ons

Level 2:
Draw the s and p – p-orbitals and state the difference between them.

Level 3:
• Use these terms to construct a concept map that organizes the major ideas of
this chapter: Aufbau's principle, energy level, quantum mechanical model, Hund's
rule of maximum multiplicity, Pauli exclusion principle, electron configuration

Level 2:
Write the electron configuration of the following elements using the ‘electron-in-
boxes’ method:
(a) nitrogen
(b) neon
(c) chlorine
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 (d) calcium
(e) scandium.
●

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