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.

Lecture Note 1: Electronic configuration, periodicity and building up of

the periodic table.
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:

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 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.

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 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.

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.

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:

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Mendeleev’s Periodic Table
The earliest version of the current form of periodic table was presented simultaneously
by Dmitri Mendeleev of Russia and Lothar Meyer of Germany. Both the scientists
arranged the elements in order of increasing atomic weights and observed that
elements with similar properties (in families) appeared at regular intervals.
Mendeleev’s periodic law stated that the physical and chemical properties of elements
are the periodic function of their atomic weights.

Important characteristics of modern version of Mendeleev’s short periodic table

are listed as follows:
I. Horizontal rows or Periods
1. First period consists of 2 elements and is known as very short period.
2. Second period consists of 8 elements and is known as -rst short period.
3. Third period consists of 8 elements and is known as second short period.
4. Fourth period consists of 18 elements and is known as -rst long period.
5. Fifth period consists of 18 elements and is known as second long period.

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6. Sixth period consists of 32 elements and is known as very long period.
7. Seventh period is an incomplete period.

II. Vertical columns or Groups

1. Group I A elements are called as alkali metals (expect H).
2. Group II A elements are called as alkaline earth metals.
3. Group V B elements are called as pnicogens.
4. Group VI B elements are called as chalcogens.
5. Group VII B elements are called as halogens.
6. Group 0 elements are called as inert gases.

III. Other features

1. Lanthanides or Lanthanoids or Rare earths: These include elements from Ce (58)
to Lu (71).
2. Actinides or Actinoids: These include elements from Th (90) to Lr (103).
3. Coinage metals: These include Cu, Ag and Au. These metals were once used as
currency.
4. Noble metals: These include Ag, Au, Pt and Hg. They are so called because of their
very low reactivity.
5. Transuranium metals: Elements beyond U (92) are known as transuranium metals.
6. The elements of third period are called as bridging elements because the concept
of subgroups A and B starts after this period. Also, these elements maintain some
similarities in properties with both subgroups A and B elements.
7. Diagonal relationship: There are three set of elements, that is, (Li, Mg), (Be, Al) and
(B, Si), which, though, placed in different groups, show some similarities in their
properties. This kind of similarity in properties is known as diagonal relationship and
is attributed to their similar sizes.

Modern periodic law

According to the modern periodic law, the physical and chemical properties of the
elements are the periodic functions of their atomic number. The long form of periodic
table based upon the modern periodic law is depicted in Figure below . Note that the
arrangement of A and B subgroups is different from that in the
modified form of Mendeleev's periodic table. The left and right corners of the table are
assigned as subgroups A and the middle of the periodic table is assigned as
subgroups B.

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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
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:

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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
called alkali metals while those having ns2 configuration are called alkaline earth
metals. Valence shell electrons for s-block elements is equal to the number of
electrons in the s orbital,having the highest principal quantum number.
(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. Valence shell electrons
for p-block elements are equal to the number of electrons in the s and p orbitals having
highest principal quantum number.
(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.
Prediction of period and group number of an element from its electronic
configuration
1. For the period: The highest principal quantum number available in the electronic
configuration is the period number of that element (except in the case of Pd).
2. For the group number:
a. For s-block elements: Total number of valence shell electrons is the group number
of it.

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b. For p-block element: (Total number of valence shell electron + 10) = Group number
of it.
c. For d-block element: Total number of valence shell electrons is the group number.
d. For f-block element: All elements are placed in the Group III or Group III B.

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.
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:

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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, metallic radius and
Van der Waals radius:
Covalent radius
The covalent radius of an element represents the contribution of that element to the
length of a bond that is predominantly covalent. For example, the covalent radius of
any element A is taken to be one half of the internuclear distance in the homonuclear
diatomic molecule A2 as shown below:

Metallic radius
For metals the metallic radius is de-ned as half of the internuclear distance separating
two adjacent metal atoms in a metallic lattice.

van der Waals radius

The sum of the van der Waals radii of two atoms is the shortest distance between two
immediately adjacent atoms (either of same or different elements) in the structure of
the solid compound in which they are not bonded to each other.

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Periodic variation of atomic radii
1. Variation in a period: In representative (s- and p- block) elements, there is a
general decrease of atomic radius in a period because the effective nuclear charge
(Zeff ) increases across a row. If all are van der Waals radii, then

2. Variation in a group: For representative (s- and p- block) elements, the atomic
radii increases down the group. This is due to successive use of orbitals with principal
quantum number (n) one higher than the last.
Ionic radius
When a positive ion is formed, the number of positive charges on the nucleus exceeds
the number of electrons and effective nuclear charge is increased, resulting in the
remaining electrons being attracted more strongly by the nucleus. Thus a positive ion
is always smaller than the corresponding atom and more the electrons removed
smaller is the ion.
When a negative ion is formed, one or more electrons are added to an atom and the
effective nuclear charge is reduced. The electron cloud expands and the size of
negative ion is more than that of the atom.

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Ionization energy
Ionization energy (IE) is the energy required to remove an electron from an isolated
gaseous atom in it ground state.

Ionization energy depends upon the following factors:

1. It decreases when shell number or the radius increases.
2. It increases when Zeff increases.
3. It decreases when σ (shielding constant) increases.
4. It is more for half--filled and fully--filled electronic configurations.
5. It also depends upon the orbitals from which the electron is removed. If the principal
quantum number is the same, then the energy required for removal of electrons from
different orbitals shows the following order: s > p > d > f.

Periodic variations in ionization energy

The trends in ionization energy of elements in the periodic table are discussed as
follows:

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Electron affinity

Periodic trends of electron affinity

c. In a period: The electron affinity increases from left to right as Zeff increases
(except inert gases) in a period.
Periodic variations of electronegativity
1. In a period, the electronegativity increases from left to right as Zeff increases.
2. In a group, the electronegativity decreases in general.
Some important points related to electronegativity are listed as follows:
1. Fluorine has the highest electronegativity in the periodic table, that is, 4.
2. Caesium is having lowest electronegativity in the periodic table, that is, 0.7
3. Alkali metals have the lowest electronegativity in their respective period.
4. Halogens have the highest electronegativity in their respective period.
5. Electronegativity of inert gases is zero.

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 Lecture Note 2: Hybridization and Shapes of Simple Molecules

Hybridization
Hybridization is a hypothetical concept that was introduced by Pauling and Slater.
According to this concept any number of atomic orbitals of an atom which differ in
energy slightly may mix with each other to form new orbitals called hybrid orbitals. The
process of mixing or amalgamation of atomic orbitals of nearly same energy to
produce a set of entirely new orbitals of equivalent energy is known as hybridization.
The following are the rules of hybridization:
(i) Only orbitals (atomic) of nearly same energy belonging to same atom or ion can
take part in hybridization.
(ii) Number of the hybrid orbitals formed is always equal to number of atomic orbitals
which have taken part in the process of hybridization.
(iii) Most of the hybrid orbitals are similar but they are not necessarily identical in
shape. They may differ from one another in orientation in space.
(iv) Actually the orbitals which undergo hybridization and not the electrons.
(v) The electron waves in hybrid orbitals repel each other and this tend to the farthest
apart.
(vi) Hybrid orbitals form only sigma bonds. A hybrid bond is always stronger than a
non-hybrid bond.
(vii) Depending on the number and nature of orbitals undergoing hybridization, various
types of hybrid orbitals directing towards the corners of specified geometrical figures
come into existence.
Some Typical Cases of Hybridization
(i) BeF2 molecule (inear shape): Beryllium atom has the configuration 1s2 2s2. Since
there are no unpaired electrons in the valency shell, it cannot form any covalent, bond.
Thus, 2s-orbital is first unpaired and an electron is shifted to 2p-orbital.

Now, there is hybridization between one s- and one p-orbital. Two orbitals (hybrid) of
same shape and energy come into existence. These overlap with p-orbital (singly
occupied) each of the two fluorine atoms forming two sigma bonds. The molecule
formed is linear with a bond angle 180°,

Fig. Formation of BeF2 molecule

(ii) BF3 molecule (triangular planar shape).: Boron atom has configuration 1s2 2s2
2p1. In ground state, it has one unpaired orbital which can only form only one covalent
bond. To get trivalency, the 2s-orbital is unpaired and the electron is shifted to 2p-
orbital.

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 Now in excited state the three unpaired orbitals undergo hybridization giving rise to
three hybrid orbitals which are 120° apart. The three hybrid orbitals overlap with three
p-orbitals from three fluorine atoms forming three sigma bonds. The molecule formed
is triangular and planar.

(iii) CH4 molecule (tetrahedral.shape): Carbon atom has configuration1s2 2s2 2px1
2py1. In ground state, it has two unpaired orbitals which can form only two covalent
bonds. To get tetravalency, 2s-orbital is unpaired and the electron is shifted to 2p-
orbital.

Now in excited state the four unpaired orbitals undergo hybridization giving rise to four
hybrid orbitals which are 109°28' apart. The four hybrid orbitals overlap with s-orbital
of each of the four hydrogen atoms forming four sigma bonds. The molecule formed
is tetrahedral.

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(iv) PCl5 molecule (Trigonal pyramidal shape): P-atom has configuration1s2 2s2 2p6
3s23px1 3py13pz1. In ground state, it can form three covalent bonds as three unpaired
orbitals are present in the valency shell. To get pentavalency, 3s-orbital is unpaired
and the electron is shifted to 3d-orbital.

Now, in the excited state the five orbitals involving one 8-, one d- and three p-orbitals
undergo hybridization giving birth to five hybrid orbitals which overlap with five chlorine
atoms forming five sigma bonds. Out of five a-bonds, three bonds which are located
at 120° angle are equitorial and. the remaining two are axial forming a trigonal
bipyramidal shape.

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