CHM 101: General Chemistry I

1st Semester 2023/2024

Lecture note
Content
• Lecture Note 1: Electronic configuration, periodicity and building up of
the periodic table.
• Lecture Note 2: Hybridization and shapes of simple molecules.

The quantum mechanical model of an atom

Early models of the atom had electrons going around the nucleus in a random fashion.
But later discoveries have shown that this representation was not accurate. Today,
scientists use the quantum mechanical model, a highly mathematical model, to
represent the structure of the atom.
This model is based on quantum theory, which says that matter also has properties
associated with waves. According to quantum theory, it is impossible to know an
electron’s exact position and momentum (speed and direction, multiplied by mass) at
the same time. This is known as the uncertainty principle. Based on this, scientists
developed the concept of orbitals which are volumes of space in which an electron is
likely present.
The quantum mechanical model of the atom uses complex shapes of orbitals and four
numbers, called quantum numbers, to describe the characteristics of electrons and
their orbitals. Accordingly, an electron in an atom can be described by four quantum
numbers based on this model. This are namely:
1. Principal quantum number (n)
2. Angular momentum quantum number (l)
3. Magnetic quantum number (ml)
4. Spin quantum number (ms)

1. Principal quantum number (n)

The principal quantum number n describes the average distance of the orbital from
the nucleus — and the energy of the electron in an atom. n represents the number of
the shell (orbit) or main energy level in which the electron revolves round the nucleus.
It can have only positive integer (whole number) values: 1, 2, 3, 4, etc. which
represents 1st(K), 2nd(L), 3rd(M), 4th(N) etc. shells. The larger the value of n, the
higher the energy and the larger the orbital, or electron shell.

2. Angular momentum quantum number (l)

The Angular momentum or Azimuthal quantum number describes the shape of the
orbital occupied by the electron. The possible values which l can have depend on the
value of n. l may have values from 0 to (n-1), i.e. 0, 1, 2, … (n – 1). Each value of l
represents a particular sub-shell within the principal sub-shell. Thus:
Value for l 0 1 2 3 4
Notation for s p d f g
subshell

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 Orbital Spherical Dumbbell Double six-sided eight-
Shape dumbell shape sided
shape

Each shell also has one or more subshells which depend on the value of n. Thus the
total number of l values gives us the total number of subshells within a given main
shell. When a particular subshell in an atom is being described, both the n value and
the subshell letter can be used e.g., 1s, 2p, 3d, and so on. Normally, a subshell value
of 4 is the largest needed to describe a particular subshell.
n 1 2 3 4
l values 0 0, 1 0, 1, 2 0, 1, 2, 3

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 subshells 1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f

3. Magnetic quantum number (ml)

The magnetic quantum number ml describes how the various orbitals are oriented in
space. The value of ml depends on the value of l. It is given by the formula 2l + 1. The
values allowed are integers from –l to 0 to +l. 2
For example, if the value of l = 1 (p orbital), you can write three values for ml: –1, 0,
and +1. This means that there are three different p subshells for a particular orbital.
For l = 2 (d orbital), you can write five values for ml: -2,1,0,1,2 This means that there
are five different d subshells for a particular orbital. The subshells have the same
energy but different orientations in space. Table below gives the different values of n,
l and ml.

The spin quantum number (ms)

The fourth and final quantum number is the spin quantum number ms. It describes the
direction the electron is spinning in a magnetic field — either clockwise or counter-
clockwise. Only two values are allowed for ms: +1⁄2 or –1⁄2. For each subshell, there
can be only two electrons, one with a spin of +1⁄2 and another with a spin of –1⁄2.

Electronic Configurations and the Periodic Table

The electronic configuration of the atoms of elements provide a theoretical foundation
for the classification of elements. It is now recognised that the periodic table is
essentially the consequence of the periodic variation in electronic configuration of the
atoms of the elements which determines the physical and chemical properties of the
elements and their compounds.
Rules for filling electrons in orbitals
1. Aufbau Rule
According to the rule, “electrons in various sub-orbits of an orbital are filled in the
increasing order of their energies". The assignment of all the electrons in an atom into
specific shells and subshells is known as the element’s electron configuration. This
follows what is known as the (n + l) rule. The main tenets of the rule are as follows:
a. Higher the value of (n + l) for a given orbital, greater is its energy. For example,
4s (n + l = 4 + 0 = 4) is has higher energy than 3s (n + l = 3 + 0 = 3)
b. If (n + l) value for two orbitals are same, then the orbital with higher value of n
will have higher energy. For example, in 4s orbital; (n + l = 4 + 0 = 4) and in 3p
orbit; (n + l = 3 + 1 = 4). Both orbitals have same (n + l) values, therefore 4s will
have higher energy than 3p orbital due to higher value of n.

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Thus, the order in which the energies of the sub-orbits increase and hence the order
in which the sub-orbits are filled is as follows:

The figure below shows the increasing order of energy

2. Hund’s rule of maximum multiplicity

According to the rule, “Pairing of electrons in various orbitals of a sub-orbit takes place
only after each orbital is half-filled/singly occupied."
This is an empirical rule that determines the lowest energy arrangement of electrons
in a subshell. It implies that pairing of electrons in orbitals of p, d and f subshells does
not take place till each orbital belonging to that subshell has got one electron each.
Since there are three p, five d and seven f orbitals, the pairing of electrons in them
would begin with the 4th, 6th and 8th electron, respectively. This is because half-filled
and completely filled states are associated with extra stability.

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3. Pauli’s exclusion principle
According to the principle, "No two electrons in an atom can have the same set of
quantum numbers." This determines the maximum of 2, 6, 10, 14 electrons
respectively in s,p,d,f sub-orbits. Three quantum numbers n, l and ml are needed to
describe an orbital. Each orbital may hold up to two electrons, provided they have
opposite spins. In addition, an extra quantum number is required to define the spin of
an electron in an orbital. Thus, four quantum numbers are needed to define the energy
of an electron in an atom. For example, two electrons in Is2 (helium) have same values
of n, I, m but they differ in spin. Hence, the two electrons do not have the same set of
four quantum numbers.

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Building up of the periodic table

Writing Electronic Configuration

Electronic configuration of atoms is the distribution of electrons into atomic orbitals.
When atoms are in their ground state, the electrons occupy the lowest possible energy
levels. This is shown in the illustrated figures below.

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To show the positions of the electrons in an atom, the symbols 1s, 2s, 2p, etc. are
used to denote the main energy level and sublevel. A superscript indicates the number
of electrons in each set of orbitals. Thus for hydrogen, the 1s orbital contains one
electron, and this is shown as 1s1. For helium, the 1s orbital contains two electrons,
denoted 1s2. After the 1s, 2s, 2p, 3s and 3p levels have been filled at argon, the next
two electrons go into the 4s level. This gives the elements potassium and calcium. The
electronic structures of the first twenty atoms in the periodic table may be written as
shown.

An alternative way of showing the electronic structure of an atom is to draw boxes for
orbitals, and arrows for the electrons (Fig. 2.3.). By convention, electron spins are
represented by arrows pointing up (↑) or down (↓). The orbital diagram for electronic
configuration is more beneficial as all the four quantum numbers are represented by
it.
Sometimes, the electronic configuration of an element is written in a shorthand form.
This is because we are interested primarily in the electrons of the outer shell, thus, we
often write electron configurations in an abbreviated or shorthand form. To write the
shorthand configuration for an element we indicate what the core is by placing in
brackets the symbol of the noble gas whose electron configuration is the same as the
core configuration. This is followed by the configuration of the outer electrons for the
particular element. Thus, for sodium and magnesium we write:

Classification of Elements in the periodic on the basis of electronic

configuration
Elements in the periodic can be classified based on the (1) Bohr’s classification, and
the (2) Differentiating electron classification

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1. Bohr's Classification
The classification proposed by Bohr is based on complete and incomplete energy
shells. The elements have been grouped into four types as follows:
(i) Inert gasses: In the atoms of these elements, the s- and p- subshells of the
outermost shell are completely filled. With the exception of helium which has 1s 2
configuration, all others have ns2 np6 configuration. These elements are also called
noble gasses.
(ii) Representative or Normal elements: In these elements atoms have all shells
complete except outermost shell which is incomplete. The number of electrons in the
outermost shell varies from 1 to 7, i.e., the configuration of the outermost shell varies
from ns1 to ns2 np5. The number of electrons present in the outermost shell signify the
group to which these elements belong.
(iii) Transition elements: In the atoms of these elements the outermost shell and the
penultimate shell (next to the outermost) are incomplete. These elements have the
general configuration (n-1)d1 -9 ns0 or 1 or 2 either in the ground state or in excited state.
(iv) Inner-transition elements: Atoms of these elements have three outermost shells
incomplete. The general configuration is (n -2)f 1-14 (n - l)d0 or 1 ns2.
These classifications are shown in the periodic table shown below:

2. Differentiating Electron Classifications. (Division of elements into s-, p-, d-, f-

Blocks)
This classification divides the elements into four types, i.e., s-, p-, d- and f-block
elements depending on the nature of the atomic shell into which the last electron
enters. The last electron is called as differentiating electron. This classification is most
rational and is now commonly in use.

(i) s-Block Elements: In these elements, the last electron enters the ns energy shell
and they have valency shell configuration either ns1 or ns2. The members of this block
lie on the extreme left of the periodic table. The elements having ns1 configuration are

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called alkali metals while those having ns2 configuration are called alkaline earth
metals.

(ii) p-Block Elements: In the atoms of these elements, the last electron enters the
p-supshell of the outermost shell In these elements np subshell is gradually 'filled, up.
The valency shell configuration varies from ns2np1 to ns2 np6.

(iii) d-Block Elements: The d-block elements are also called transition metals. In
these elements, the last electron enters (n - l) d-subshell (d-orbitals of the penultimate
orbit), i.e., (n -1) d-subshell is gradually filled up.
(iv) f-Block Elements (Inner-Transition Elements) In these elements the last
electron enters the (n - 2) f energy shell fI-orbitals of the (n - 2) main shell, i.e., (n - 2)
f subshell is gradually filled up.
These block of elements are shown in the periodic table below.

Periodic Classification of Elements: Periodicity in Properties

The reoccurrence of similar properties of the elements after certain definite intervals
when the elements are arranged in the order of increasing atomic numbers in the
periodic table is termed periodicity. The cause of periodicity is the repetition of similar
electronic configuration of the atom in the valence shell after certain definite intervals.
These definite intervals are 2, 8, 8, 18, 18 and 32. Periodicity is observed in a number
of properties which are directly or indirectly linked with electronic configuration Some
of the properties which depend on electronic configuration of elements such as
screening effect, effective atomic number, atomic radii, ionic radii, ionisation potential,
electron affinity, electronegativity, etc
Two factors that affect the periodic properties of elements are the screening effect and
effective nuclear charge.
The screening effect or shielding effect: The decrease in the force of attraction
exerted by the nucleus on the valency electrons due to the presence of electrons in
the inner shells, is called screening effect or shielding effect. The magnitude of the
screening effect depends upon the number of inner electrons, i.e., higher the number
of inner electrons, greater shall be the value of screening effect. The screening effect
constant is represented by the symbol σ.

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Effective Nuclear Charge: This refers to the net positive charge pulling electrons
towards the nucleus. It is represented by the symbol Z. Due to screening effect the
valency electron experiences less attraction towards nucleus. This brings decrease in
the nuclear charge (Z) present on the nucleus. The reduced nuclear charge is termed
effective nuclear charge and is represented by Z*. It is related to actual nuclear charge
(Z) by the following formula:
Z * = (Z - σ), where σ is screening constant.
The periodicity or periodic trends in some properties
The periodicity or periodic trends in some properties such as atomic radii, ionisation
energy or enthalpy, electronegativity are discussed as follows:
1. Atomic Radius:
An atom is assumed to be spherical in shape and, thus, the size of atom is generally
given in terms of radius of the sphere and is called atomic radius. It is usually defined
as the distance between the centre of the nucleus and outermost shell where electron
or electrons are present. The exact measurement of atomic radius is difficult because
the size of an atom is small, and it does not have well defined boundaries. In addition,
it is also not possible to get an isolated atom.
There are three types of atomic radius namely Covalent radius crystal radius and Van
der Waals radius: A comparison of covalent and van der Waals radius is shown below.

Variation of Atomic Radii

(a) Variation in a Period: As we move from left to right across a period, there is regular
decrease in atomic radii of the representative elements. This is due to the fact that
number of energy shells remain the same in a period but nuclear charge increases
gradually as the atomic number increases. This increases the force of attraction
towards nucleus which brings contraction in size. This can also be explained on the b
(b) Variation in a Group: Atomic radii in a group increase as the atomic number
increases. The increase in size is due to extra energy shells which outweigh the effect
of increased nuclear charge. The following table illustrates the effect in the periodicity
in atomic radii (covalent radii) of representative elements.

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2. Ionization Energy:
The electrons in an atom are attracted by the positive charge present on the nucleus.
To remove an electron from an atom, energy has to be supplied to overcome the force
of attraction towards nucleus. A quantitative measure of the tendency of an atom of
an element to lose electron is given by its ionisation enthalpy. It is defined as the
minimum amount of energy required to remove most loosely bound electron from an
isolated atom in the gaseous state of an element so as to convert it into gaseous
monovalent positive ion. It is also known as first ionisation energy. Like the removal of
first electron from isolated gaseous atom, it is possible to remove second, third and
successive electrons from positive ions one after the other. The amounts of energies
required are termed second, third, fourth etc ionisation enthalpies respectively.
Variation of Ionisation energy
(a) Variation in a Period: Ionization energy increases across a period (on moving left
to right) As we move across a period, the atomic radii decrease, and the effective
nuclear charge increases. So, the external electrons are held nearer to the nucleus
and all the more emphatically pulled into the middle. Thus, it becomes harder to
remove an electron from the atom. Hence, more ionization energy is required.
(b) Variation in a Group: Ionization energy decreases (on moving up to down) down
the group .As we move down the group, the atomic size increases and effective
nuclear charge decreases as the outermost electrons are further away from nucleus.
Thus, it becomes easy to remove an electron from the atom. Hence, less ionization
energy is required.

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3. Electronegetivity:
The tendency of an atom in a molecule to attract the shared pair of electrons towards
itself is known as electronegativity.It is a dimensionless property because it is only a
tendency. It basically indicates the net result of the tendencies of atoms in different
elements to attract the bond-forming electron pairs.
(a) Variation in a Period: As we move across a period from left to right the nuclear
charge increases and the atomic size decreases, therefore the value of
electronegativity increases across a period in the modern periodic table.
(b) Variation in a Group: There is an increase in the atomic number as we move down
the group in the modern periodic table. The nuclear charge also increases but the
effect of the increase in nuclear charge is overcome by the addition of one shell.
Hence, the value of electronegativity decreases as we move down the group.

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