Chemical Bonding (Basic Concepts)

Prepared by: Md. Mohsin Uddin Azad

Assistant Professor (Chemistry)
Department of Textile Engineering
Northern University Bangladesh (NUB)

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Chemical Bonding: General Concepts

Chemical Bonds are forces that hold groups of atoms or ions together and make them function as a unit

Types of Chemical Bonds

 Ionic bonds - electrostatic attractions between cations and anions in ionic crystals;
 Covalent bonds – shared electron-pairs that hold two atoms (usually two nonmetal atoms or a
semimetal and nonmetal) together.

Ionic Bonds
In the formation of an ionic compound, one or more electrons are transferred from the metal to nonmetal
atoms. For example, in the reaction between sodium and chlorine, an electron is transferred from a Na to Cl
atoms. Electrostatic attractions between the resulting ions constitutes ionic bonds.

The Formation of Stable Ions and Electron Configurations of Ions

With the exception of helium, each of the other noble gas atom has eight (8) electrons in the outermost
shell with the electron configuration ns2np6, where n is the principal quantum number of the outermost shell.
G.N. Lewis believed that this configuration, where the s- and p-subshells of the outermost shell are completely
filled (with eight electrons), represents the most stable state for an element. It is called an octet state. Lewis
introduced the electron-dot symbols which show the number of valence electrons in atoms.

Lewis "Electron-dot" Symbols for Atoms of the Second Period

————————————————————————————————————————
IA IIA IIIA IVA VA VIA VIIA VIIIA
————————————————————————————————————————
Li Be B C N O F Ne

2s1 2s2 2s22p1 2s22p2 2s22p3 2s22p4 2s22p5 2s22p6

Na Mg Al Si P S Cl Ar

3s1 3s2 3s2 3p1 3s2 3p2 3s2 3p3 3s2 3p4 3s2 3p5 3s2 3p6
————————————————————————————————————————

To acquire the octet state, an atom of the main group element may lose or gains a certain number of
electrons and becomes ion. Electrons are lost from or added to the valence shell. For example:

Na ([Ne]3s1)  Na+ ([Ne]) + e-;

Cl ([Ne]3s23p5) + e-  Cl- ([Ar])
—————————————————————
Species: Na + Cl  Na+ + Cl-  NaCl
e-config.: [Ne]3s1 + [Ne]3s23p5 [Ne] + [Ar]

Thus, an atom loses or gains one or more electrons to become an ion and acquires the noble gas electron
configuration - ns2np6. Isoelectronic ions that have acquired the octet state and the noble gas electron
configurations are listed below:

Ions isoelectronic to [Ne] = 1s2 2s2 2p6 : Na+, Mg2+, Al3+, F-, O2-, and N3-;
Ions isoelectronic to [Ar] = 1s22s22p63s23p6 : K+, Ca2+, Sc3+, Cl-, S2-, and P3-
Ions isoelectronic to [Kr] = 1s22s22p63s23p64s23d104p6 : Rb+, Sr2+, Y3+, Br-, and Se2-;
Ions isoelectronic to [Xe] = 1s22s22p63s23p64s23d104p65s24d105p5: Cs+, Ba2+, La3+, I-, and Te2-;

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Ionic Sizes
Like atomic sizes, the size of ions with similar charges increases down the group. For isoelectronic ions,
the size decreases with increasing positive charges and increases with increasing negative charges. For example,
the trend of ionic sizes for the following group of ions is: O2- > F- > Na+ > Mg2+ > Al3+. That is, for isoelectronic
species, ion with the most negative charge is the largest and one with the most positive charge is the smallest. In
going from O2- to Al3+, effective nuclear charges increase while electron-electron repulsions remains fairly
constant. Therefore, ionic sizes decreases as a result of increasing effective nuclear charge, which pulls electron
cloud closer to the nucleus.

Types of Covalent Bonds:

1. Polar covalent bond - occurs when bonded atoms have different electronegativity and bonding electrons
are displaced towards the more electronegative atom, thus creating a dipole moment and partial ionic
character.

2. Nonpolar covalent bond - formed between atoms with the same electronegativity, so that the bonding
electrons are equally shared and the bonds have no dipole moment.

3. Coordination covalent bond – this is a type of covalent bonds in which the pair of bonding electrons
originate from one of the bonded atoms (or molecule) rather than each atom contributes an electron to the
bonding pair.

Covalent Bonding:
A covalent bond can be described as a pair of electrons shared by two atoms.
E.g.
lone pair e- is the electron pairs that are not
.. .. .. .. .. .. involved in bonding.
Cl . + . Cl . Cl or
.. . ..
Cl Cl Cl
..

..

..
..

..

..

.. .. .. ..

Bond pair e-
is a pair of electrons shared between atoms in a covalent bond.
The sharing of a single pair of electrons between bonded atoms produces a single covalent bond.
The sharing of two pairs of electrons between bonded atoms produces a double covalent bond. E.g.
.. .. .. ..
. O . + .O O O
.

.. .. .. ..
The sharing of three pairs of electrons between bonded atoms produces a triple covalent bond. E.g.
.. .. .. ..
. N . + .N N N
.

. .
Coordinate Covalent Bonds
A covalent bond in which a single atom contributes both of the electrons to a shared pair is called a coordinate
covalent bond.
E.g.

Polar Covalent Bonds

A polar covalent bond is a covalent bond in which electrons are not shared equally between two atoms.
E.g.
.. 
H
+
Cl
..
..

.. + = partial positive charge

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In HCl molecule, Cl (more EN) attracted electrons more strongly than does H. The electron charge density is
greater near the Cl atom than H atom. The center of negative charge lies closer to the Cl nucleus than the center
of positive charge. We say that there is a separation of charge in H-Cl bond and that the bond is polar.

Exceptions to the Octet Rule:

1. Species with odd number of electrons, such as NO and NO2.

2. Species with less than 8 electrons around an atom - this is referred to as incomplete octet. Examples are
species such as BeCl2 and BF3, which central atoms contain 4 and 6 electrons, respectively. Species with
incomplete octets are called Lewis acids (electron-pair seekers)

3. Species with more than 8 electrons around an atom - this is referred to as an expanded octet. Examples
are: PCl5, SF4, SF6, BrF5, XeF2, and XeF4. They involve species containing elements of the third period or
higher which have empty (n-1)d orbitals in their valence shell.

Molecular Geometry

Valence-Shell Electron-Pair Repulsion (VSEPR) Theory

 VSEPR Theory focuses on molecular shapes based on the geometrical orientations of electron-pairs
about the central atom in covalent molecules.

 It is based on the concept that electron-pairs repel one another,

The order of repulsion is such that:
(Lone-pair vs. Lone-pair) > (Lone-pair vs. Bond-pair) > (Bond-pair vs. Bond-pair)

 Electron pairs assume orientations about the central atom in such a way that repulsions are minimized.
Thus, a molecular shape with minimum electron-pair repulsions is the most favored.

Hydrogen bonding is a kind of Van der Waals' forces. It is exactly the same as dipole-dipole interaction; it just
gets a special name. A hydrogen bond is a dipole-dipole interaction that occurs between any molecule with a
bond between a hydrogen atom and any of oxygen/fluorine/nitrogen. So, Hydrogen Fluoride (HF), Water (H 2O),
ammonia (NH3)....any kind of substance that has hydrogen bonded to either an oxygen, fluorine or nitrogen
atom, exhibits hydrogen bonding. The hydrogen bond is just the dipole-dipole force but it is extremely strong
compared to either dipole-dipole forces like HCl. It is extremely strong because F N and O are extremely good
at attracting electrons and H is extremely good at losing them. So basically, the bond is EXTREMELY a one-
sided affair, resulting in an extreme dipole situation, thus named, a hydrogen bond.

The evidence for hydrogen bonding

Many elements form compounds with hydrogen - referred to as "hydrides". If you plot the boiling points of the
hydrides of the Group 4 elements, you find that the boiling points increase as you go down the group.

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The increase in boiling point happens because the molecules are getting larger with more electrons, and so van
der Waals dispersion forces become greater.

If you repeat this exercise with the hydrides of elements in Groups 5, 6 and 7, something odd happens.

Although for the most part the trend is exactly the same as in group 4 (for exactly the same reasons), the boiling
point of the hydride of the first element in each group is abnormally high.