CHM 121: Foundation Chemistry I

1st Semester 2022/2023

Lecture Note
Quantum Numbers
Introduction
The atom is the smallest part of matter that represents a particular element. For quite
a while, the atom was thought to be the smallest part of matter that could exist. But in
the latter part of the 19th century and early part of the 20th, scientists discovered that
atoms are composed of certain subatomic particles and that no matter what the
element, the same subatomic particles make up the atom. The number of the various
subatomic particles is the only thing that varies. Scientists now recognize that there
are many subatomic particles. But chemists are generally concerned with the three
major subatomic particles namely: Protons, Neutrons and Electrons. Atoms have a
nucleus — a centre — containing protons and neutrons.
Many of the important topics in chemistry, such as chemical bonding, the shape of
molecules, and so on, are based on where the electrons in an atom are located. Three
things are important to understand how electron distributes itself in atom; the shape of
the orbital in which it is located, its size, and its orientation in space relative to other
orbitals. Thus, simply saying that the electrons are located outside the nucleus is not
good enough.
The quantum mechanical model
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

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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
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
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.

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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.

Fig showing electron in orbitals and subshells

Solved Examples
1. Determine the four quantum numbers for the following:
(a) the last electron in 2p5
(b) the last electron in 3d6
Solution
1(a) For 2p5
- Principal quantum number n = 2.
- Angular momentum quantum number l = 1.
- Magnetic quantum number ml = 0, since for l =1 (p orbital), the three values
for ml are –1, 0, and +1. And the last electron will be placed under py i.e ml
value of 0
↑↓ ↑↓ ↑
-1 0 1

- Spin quantum number ms = +1⁄2

1(b) For 3d6

Principal quantum number n = 3
Angular momentum quantum number l = 2
Magnetic quantum number ml = -2
Spin quantum number ms = -1⁄2

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Electronic Arrangements of Atoms
Aufbau Principle
In the case of atoms, electrons occupy the available orbitals in the subshells of lowest
energy. This is known as the Aufbau principle. 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:
1. 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)
2. If (n + l) value for two orbitals are same, then the orbital with higher value of n
will have higher energy. For example 4s (n + l = 4 + 0 = 4) and 3p (n + l = 3 + 1
= 4) have same (n + l) values, therefore 4s will have higher energy than 3p
orbital due to higher value of n.

The sequence in which the energy levels are filled is shown below;
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, etc.

Hund’s Rule of Maximum Multiplicity

Hund’s rule states that where orbitals are available in degenerate sets, maximum
multiplicity is preserved; that is, electrons are not paired until each orbital in a
degenerate set has been half-filled. 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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Pauli’s Exclusion Principle
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. 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. The Pauli
exclusion principle states that no two electrons in one atom can have all four quantum
numbers the same. By permutating the quantum numbers, the maximum number of
electrons which can be contained in each main energy level can be calculated.

The maximum electron population per shell is shown below.

This trend shows that the maximum electron population of a shell is 2n 2.

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Electronic arrangement in the first twenty elements
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 illustrated in fig 2.1 for n values of 1 to 3.

Figure 2.1 Quantum numbers, the permissible number of electrons and the shape of
the periodic table.
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.

Figure 2.2: Periodic table of elements listing the electronic configurations

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

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configuration is more beneficial as all the four quantum numbers are represented by
it.

Figure 2.3: Periodic table of elements listing the electronic structure of an atom
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:

Assignment
1. Determine the four quantum numbers for the following
(a) the last electron in 3d7
(b) all the electrons present in the outermost orbit of neon.
2. An electron is in 6f orbital. What possible values of quantum numbers n, l, ml
and ms can it have?
3. What designation is given to an orbital having:
(a) n = 2, l = 1
(b) n = 3, l = 0
4. Which of the following orbital diagrams is excluded by the Aufbau principle?
Which by the Pauli exclusion principle? Which by Hund’s rule? Which is
correct?

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5. Using s, p, d, f notations, describe the orbital with the following quantum
numbers:
(a) n = 2, l = 1
(b) n = 4, l = 0
(c) n = 5, l = 3
(d) n = 3, l = 2
6. What is the maximum number of electrons that may be present in all the atomic
orbitals with principle quantum number 3 and azimuthal quantum number 2?

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