Chemical bonding

Chemical bonding refers to any interaction that account for association of atoms into
molecules, ions and other stable species. When atoms approach one another for a
successful chemical bonding interactions, their electrons and nuclei interact and
distribute in space such that the bonding energy is lower than the sum of the energies
of the component atoms. A chemical bond is an attraction between two or more atoms
that allows the formation of chemical species such as molecules, ions and crystals. A
bond contains two electrons emanating from either electron sharing or transfers
between the participating atoms. Chemical bonding enables atoms to achieve a stable
electronic configuration. However, elements such as noble gases with already stable
electronic configuration do not take part in chemical bonding due to their completely
filled outermost electron shell. Atom may attain a stable electronic configuration either
by transfer (lost or gain) or by sharing of electrons.

Types of Chemical Bonding

The various types of chemical bond resulted from different behaviors of the outermost
or valence electron of atoms. These include:

(i) Ionic bonding (ii) Covalent bonding (iii) Metallic bonding

Metal (electropositive element) + non-metal (electronegative element) → ionic bonding

(electron transfer)

Non-metal (electronegative element) + non-metal (electronegative element) →

Covalent bond (electron sharing)

Metal (electropositive element) + metal (electropositive element) → Metallic bonding

(electron pooling)

Few bonds are purely ionic, covalent or metallic. Most are intermediate between the
three main types of bonds, and show some properties of at least two of the three types.

Lewis Symbols and the Octet Rule

Lewis dot symbol is used to depict the outer shell electron as dots around the symbol
for the element. In a Lewis electron-dot symbol (named after an American chemist G. N.
Lewis), the element symbol represents the nucleus and inner electrons, and dots around
the symbol represent the valence electrons. Valence electrons are the outermost
electrons in an atom.
 Practice Question: Give the Lewis dot symbol of the following elements (i)
Potassium (ii) Calcium

Ionic Bonding

Ionic bonding involves the transfer of electron(s) from metal atom to non-metal atom to
form ions that attract each other and form a solid compound. An ionic bond originates
from bonding pattern in which electrons are transferred from the valence shell of one
atom to the valence shell of another. The atom that loses electrons becomes a cation (a
positive ion), while the atom that gains electron(s) becomes an anion (a negative ion).
Ionic bonds exist between the metals in group I and II and the non-metals in group VIA
and VIIA. Also, the anions of certain acids, especially the oxygen acids, can form ionic
compounds with group I and II metals.

Formation of Ionic bonding

Metals lose electrons to match the number of valence electrons of their nearest noble
gas while non-metal gain electrons to attain their nearest noble gas electron
configuration.

Group 1 metals: M – e- → M+ Group 2 metals: M – 2e- → M2+

Group 17 non-metal: X + e- → X-
Practice question: Use partial orbital diagrams and Lewis symbols to depict the
formation of Na+ and O2- ions from the atoms, and give the formula of the compound
formed

Lattice Energy of Ionic Compounds

Lattice energy is the energy required to completely separate one mole of ionic
compound into gaseous ions. The lattice energy results from electrostatic interactions
among ions, so its magnitude depends on ionic size, ionic charge, and the arrangement
of the ions in the solid. The magnitude of the lattice energy is a measure of the strength
of the ionic interactions and influences macroscopic properties, such as melting point,
hardness, and solubility.

In the formation of ionic bond, the metal releases electron by accepting energy equal to
its ionization energy while the non-metal gain electrons and the energy required is
equal to the electron affinity. Therefore, the overall stability of ionic compound depends
on the interactions between the metal and non-metal. A quantitative measure of the
stability of any ionic solid is its lattice energy. One way to lattice energy is to apply
Hess’s law in a Born-Haber cycle (a series of steps from elements to ionic solid for which
all the enthalpies are known).

Considering the various steps require in the formation of LiF, Hess’s law tells that the
paths involve overall enthalpy change. ∆Hof of LiF(s) = sum of ∆Ho values for all the
multistep path.

Li(s) → Li(g) ∆Ho = 161 kJ

½F2(g) → 2F(g) ∆Ho = 79.5 kJ
Li(g) → Li+(g) + e- ∆Ho = 520 kJ
F(g) + e- → F-(g) ∆Ho = -328 kJ
Li+(g) + F-(g) → LiF(s) ∆Ho = ?
Li(s) + ½F2(g) → LiF(s) ∆Hooverall = ∆Hoformation = -617 kJ
-∆Holattice of LiF = ∆Hoformation – sum of ∆Ho of all steps
= -617 – (161 + 79.5 + 520 + (-328))
= -1050 KJ
o
∆H lattice of LiF = 1050 KJ
NOTE: The coulombic attractions between two doubly charged species, or between a
doubly charged ion and a singly charged ion, are much stronger than those between
singly charged anions and cations. The lattice energy (in KJ/mol) of MgO (3890)>Na2O
(2570)>LiF (1017)

Question: Specify which compound in the following pairs of ionic compounds has the
higher lattice energy: (a) KCl or MgO, (b) LiF or LiBr, (c) Mg3N2 or NaCl.

Covalent Bonding

A covalent bond is a chemical bond that involves the sharing of electron pair between
atoms. This electron pair is also called the bonding pair or shared pair. For many
molecules, the sharing of electrons allows each atom to attain the equivalent of a full
outer shell; corresponding to a stable electronic configuration. Covalent bonding
includes many kinds of interactions such as σ bonding and π bonding. A covalent bond
arises from the balance between the nuclei attracting the electrons and electrons and
nuclei repelling each other. Formation of a covalent bond always results in greater
electron density between the nuclei.

Single covalent bond: A shared electron pair between atoms give a single bond. An
example of such is the formation of homonuclear diatomic molecule of H2 in which each
hydrogen contribute s1 electron to give a complete s2 configuration and the electron
pair is equally shared between the two hydrogen centers.

A comparable covalent bond can be formed in HF: H +F → HF and F2: F +F → F2

Polyatomic covalent Molecules: Methane, ammonia and water molecules are among
simple covalent polyatomic molecules, in which their central atom is surrounded by
single bonds.

Methane (CH4): The valence electron of carbon in methane is given as

CH4 ≡ C – 2s22p2 + 4H – 1S1

Total valence electrons of C is 4 + (4x1)≡ 8

Electrons ≡ s2 p6

Lewis Structure of methane

Each of the four H atoms involves a shared s2[He], inert gas configuration and the one
carbon atom involves a shared s2p6 configuration of four electron pairs shared with four
separates H atoms.

Multiple Bond: Sometimes, atoms share more than one electron. Occasionally, they can
share 2 or even 3 electrons. Multiple bond arises when atom share two or three
electrons with another atom. If two or three electrons are shared, it gives double or
triple bonds respectively. A double bond contains one σ bond and π bond while a triple
bond contains one σ bond and two π bonds.

Coordinate covalent bond: A coordinate covalent bond also known as dative bond is one
in which both bonding electrons are from one of the atoms involved in the bonding. In
this form of covalent bonding, an atom will donate lone pair of electrons for sharing.
This bond gives rise to the formation of some Lewis acids and bases. Such bonding
occurs in molecules such as the NH4+, H3O+ and H3BNH3. Ammonia is a polyatomic
molecule which is formed via ordinary covalent bond. However, ammonium ion is
formed from ammonia through dative bonding with hydrogen ion. The hydrogen ion
bonds to the lone pair of electrons on the ammonia molecule to form ammonium ion.
Polar Covalent bond: A polar covalent bond is a covalent bond with a significant ionic
character. It occurs when electrons are shared unequally between atoms. This implies
that the electrons are closer to one of the atoms than the other, creating an imbalance
of charge. The electronegativity of these bonds is between 0.4 to 1.7. Water is a polar
molecule because oxygen is more electronegative than hydrogen, and therefore
electrons are pulled closer to oxygen.

Non-polar Covalent bond: This occurs when electrons are shared almost equally or
equally between atoms. Examples include H2, Cl2, NH4+ etc. All homonuclear diatomic
molecules form non-polar covalent bond. The electronegativity of these bonds ranges
from 0 to 0.4.

Properties of a Covalent Bond

A covalent bond has three important properties that are closely related to one another
and to the compound’s reactivity—bond order, bond energy, and bond length.

Bond order: The bond order is the number of electron pairs being shared by a given pair
of atoms.

Bond Order = ½ (bonding electrons – antibonding electrons).

It determines the number of bond between two atoms. The bond order can also be used
to predict the stability of molecules. If the bond order is zero, the molecule is unstable.
Bond order greater than zero suggest a stable molecule. The higher the bond order is,
the more stable the bond.

Bond energy: It is the energy needed to overcome this attrac tion and is defined as the
standard enthalpy change for breaking the bond in 1 mol of gaseous molecules. Bond
breakage is an endothermic process, so bond energy is always positive:

Bond length: A covalent bond has a bond length; and it is define as the distance
between the nuclei at the point of minimum energy
Bond Character: Bond character is determined by the difference in electronegativity
(∆EN) between the atoms that form the bond. For example Li-F bond has a ∆EN of 3.0
and is an ionic bond that is ionic in character. A notable exemption to this rule is the H-F
bond in hydrogen fluoride. H-F bond is a polar covalent bond (because it involves two
non-metals) despite that its ∆EN is 1.9.

∆EN Bond Character

0-0.4 Non polar covalent bond
0.4-1.7 Polar covalent bond
>1.7 Ionic bond
Question: Predict the nature of the bond between the following pairs of atoms as
predominantly non-polar covalent, polar covalent or ionic.

(a) S-O (b) C-O (c) Al-F

Metallic bond

Metallic bonding is the force of attraction between valence electrons and the metal
ions. It involves sharing of many detached electrons between many positive ions, where
the electrons act as a "glue" giving the substance a definite structure. Most atoms that
form metallic bond are good conductors at all state, lustrous with high melting point.
Examples are Fe, Al, Au, Co etc.

Bond Theory

Lewis bonding Theory

It is one of the simplest bonding theories that emphasize on valence electron to explain
bonding. It is described through Lewis structure models. The theory explains that
electrons are transferred or shared such that each atom attains octet arrangement.
Lewis bonding theory predicts many properties of molecules such as molecular stability,
formal charge, shape and polarity.

Lewis dot structure of CO2 and H2O

Formal Charge: It is the charge assigned to an atom in a molecule, assuming that

electrons in all chemical bonds are shared equally between atoms regardless of relative
electronegativity. When determining the best Lewis structure for a molecule, the
structure is chosen such that the formal charge on each atom is as close to zero as
possible.

Formal charge (FC) = V – N - B/2

V is the number of valence electrons of the neutral atom in isolation

N is the number of non-bonding valence electrons on this atom in the molecule

B is the total number of electrons shared in bonds with other atoms in the molecule.

For example CO2, the formal charge of C and oxygens in CO2 is calculated as;

FC of C = 4- 0 – 8/2 = 0

FC of O = 6 – 4 – 4/2 = 0

Question: Draw the Lewis structure including formal charge for SO42-, NH4+, NO2- and
NO2.

Valence Shell electron pair repulsion (VSEPR) Theory

It predicts the molecular shapes and geometry. It involves the arrangement of electron
in space to minimize electron-electron repulsion.

How to predict shape and geometry using VSEPR theory

1. Draw the Lewis structure for the molecule

2. Count the total number of bonds and lone pair around the central atom

3. Arrange the bond and lone pair in a standard geometry to minimize electron-electron
repulsion. Lone pair electrons stay closer to the nucleus and spread over a larger space
than the bonding pair. Hence large angles are found between lone pairs
LP-LP > LP-BP > BP-BP (repulsion tendency)

Steric Number = Number of atoms bonded to the central atom + Number of lone pairs
on the central atom

Molecules Steric No. Geometry Example

MA2 2 Linear BeCl2
MA3 3 Trigonal planar BF3
MA4 4 Tetrahedral SiF4
MA5 5 Trigonal bipyramidal PF5
MA6 6 Octahedral SF6

When considering the shape of molecules using VSEPR-theory, multiple bonds are count
as single bond region.

Bent rule: It describes the variation in geometry that could be experienced in molecules
with the same steric number. This is due to the difference in electron-elecron repulsion
ability between the bonding and non-bonding electrons, and the fact that more
electronegative substituent “prefer” hybrid orbital having less s-character, and more
electropositive substituent prefer having more s-character.

For example, CH4, NH3 and H2O are MA4 molecules with steric number of 4. They are all
expected to have tetrahedral shape (109.5⁰) but only methane is tetrahedral among
them. NH3 is pyramidal (107.3⁰) while H2O is bent (104.5⁰).

Question: Predict the shape of the following molecules using VSEPR-theory i. H2O

ii. NH4+ iii. BCl3 iv. CO2

Limitation of VSEPR-Theory

1. Its fails to predict the shapes of isoelectronic species and transition metal compounds

2. It does not take relative sizes of substituent and stereochemically inactive lone pairs
into account

3. It cannot be applied to heavy d-block species that experience stereochemical inert

unit pair effect

Valence Bond Theory

Valence bond (VB) theory assumes that all bonds are localized bond which is formed
between atoms by donation of electron from each atom. It also assumes that the
sharing of electrons between atoms is viewed as an overlapping of atomic orbitals of the
bonding atoms. VB-theory uses valence electron to describe bonding. For example, H-H
bond is formed through the overlapping of two half-filled s-orbitals.

H-H bond (H2)

H-F bond

H-1s1 ; F- 2s22px2 2py2 2pz1

Question: Describe the formation of SF6 and SF4 using valence bond theory

Hybridization: It is the mixing of atomic orbitals to form new hybrid orbitals. The hybrid
orbitals are useful in explaining molecular geometry and atomic bonding properties. The
various types of hybridized orbitals include: sp (form from mixing a “s” and a “p” orbital
to give two sp-hybrid orbitals), sp2, sp2d, sp3, sp3d, sp3d2. These hybridized orbitals have
the assigned geometry; sp-linear, sp2-planar, sp2d-square planar, sp3- tetrahedral, sp3d2-
octahedral.

σ bond and π-bond: Sigma (σ) bond is symmetric about its axis. It is formed through
head-on overlapping between atomic orbitals. However, π-bond electrons distribute
above and below the axis of the nodal plane. π-bonds are formed through side to side
overlapping of two “p-orbitals” and can only be formed from p-orbitals. π-bonds are
weaker than σ-bonds. The diagram below shows overlapping of p-orbitals to give σ bond
and π-bond.
Formation of hybridized orbitals

sp3 hybrdized orbitals: It is formed from mixing a “s“ and three “p” orbitals. Examples
are CH4, CF4, NH3 etc. Considering the hybridization in methane;

Valence of C – 2s22p2

Ground state   

2s 2p

Excited state    

2s 2p

mixed to give sp3

1s1 electron of each H will pair with the four sp3 hybrid orbitals resulting to the
formation of CH4

sp2 hybridized orbitals: It is formed from mixing a “s” and two of “p” orbitals. Examples
are BF3, H2CO, H2C=CH2 etc. Considering the formation of hybrid orbitals in ethane;

Valence of C – 2s22p2

  
Ground state

2s 2p

Excited state    

2s 2p

mixed to give sp2

Each carbon will have 3 sp2 hybrid orbitals and one unhybridized p-orbital. One of the
hybridized orbitals will overlap with that of the second carbon to give σ bond while the
unhybridized p-orbitals will overlap side to side to give π-bond.

sp hybridized orbitals: It is formed from mixing “s” and three of “p” orbitals. Examples
are BeCl2, C2H2, H2CN, CO2 etc. Considering the formation of hybrid orbitals in ethene;

Valence of C – 2s22p2

Ground state   

2s 2p

Excited state    

2s 2p

mixed to give sp

Each carbon will have 2 sp hybrid orbitals and two unhybridized p-orbitals. One of the
hybridized orbitals will overlap with that of the second carbon to give σ bond while the
unhybridized p-orbitals will overlap side to side to give two π-bonds.

Limitation of VB-theory

1. It can’t explain colour and spectra

2. It can’t explain the relative stability of structural isomers

3. It does not discus about energies of electron

Molecular Orbital Theory

The theory predicts that molecular orbitals are obtained by combining the atomic
orbitals. The common approximation that allows the generation of molecular orbital
diagram for small diatomic molecules is called the “linear combination of atomic
orbitals” (LCAO) approach. The following assumptions lie in the core of this model

1. Molecular orbitals are formed from the overlap of atomic orbitals

2. Only atomic orbitals of about the same energy interact to a significant degree

3. when two atomic orbitals overlap, they interact in two extreme ways to form two
molecular orbitals, a bonding molecular orbital and antibonding molecular orbital.

Considering the H2 molecule, one of the molecular orbitals in this molecule is

constructed by adding mathematical function for the two 1s atomic orbitals that come
together to form this molecule. Another orbital is formed by subtracting one of these
functions from the other.

One of these molecular orbitals is called the bonding molecular orbital, σ while the
other is called antibonding molecular orbital σ*. The electrons are in the region between
the two nuclei in bonding molecular orbital but away from the region in antibonding
molecular orbital.

The order of filling electrons in molecular orbital theory is as follows: σ1s, σ1s*, σ2s, σ2s*,
σ2p, π2px, π2py, π2px*, π2py*, σ2p* σ3s,…. It should be noted that π2px and π2py have the same
energy, therefore, each of the molecular orbitals have to be singly filled before being
paired up. Similar situation is found in π2px* and π2py*.

Experiments have shown that the diagram above best described the model of O 2 and
F2. However, B2, C2 and N2 are described by a model that include hybridization with the
arrangement given as, σ1s, σ1s*, σ2s, σ2s*, π2px, π2py, σ2p , π2px*, π2py*, σ2p* σ3s
Molecular orbital diagram can be used to predict whether a molecule is paramagnetic or
diamagnetic. If all the electrons are paired up, the molecule is diamagnetic. If one or
more electrons are unpaired, the molecule is paramagnetic.

Question: Write out the molecular orbital configuration of F2, Ne2, CO and NO. Calculate
the bond order of these molecules and determine whether these molecules are
paramagnetic.

Intermolecular Bonding

Intermolecular bonds have forces of attraction or repulsion that act between

neighbouring particles (atom, molecules or ions). They are weak compared to the
intramolecular forces. The various types of intermolecular forces include:
1. Dipole-dipole interactions: This results from the different in electronegativities
between two bonded atoms. This difference causes permanent charge separation.

2. Hydrogen bond: It is the attractive force between the hydrogen attached to an

electronegative atom of one molecule and an electronegative atom of a different
molecule. It occurs in molecule such as HF, H2O, NH3. Hydrogen bonding is responsible
for high boiling point of water and ammonia.

3. London dispersion forces (also known as Van der waal’s forces): This arises due to
instantaneous dipoles in neighbouring atoms. As the negative charge of the electron is
not uniform around the whole atom, there is always a charge imbalance. This small
charge will induce a corresponding dipole in a nearby molecule e.g condensation of
bromine gas.

4. Cation –π interaction: This occurs between a π-bond and a cation. This type of
interaction could be found between benzene and sodium ion.