Dr. O.

Erharuyi
CHEMICAL BONDING THEORIES: FORMATION OF CHEMICAL BONDS

Introduction

Chemical bonding is one of the most basic fundamentals of chemistry that explains other concepts such as
molecules and reactions. Without it, scientists would not be able to explain why atoms are attracted to each
other or how products are formed after a chemical reaction has taken place. To understand the concept of
bonding, one must first know the basics behind atomic structure.

An atom contains a nucleus composed of protons and neutrons, with electrons in certain energy levels
revolving around the nucleus (Figure 1). Elements are distinguishable from each other due to their "electron
cloud," or the area where electrons move around the nucleus of an atom. It is these electrons that are involved
in chemical bonding.

Electron orbits

Electron

Proton

Neutron

Figure 1: Bohr atomic model

Chemical Bonding
A bond is a link or force between neighboring atoms in a molecule or compound (Figure 2). Chemical
bonding describes a variety of interactions that hold atoms together in chemical compounds. It is the
attractive force that holds two atoms together. Atoms form bonds in order to obtain a stable electronic
configuration, i.e. the electronic configuration of the nearest noble gas. All noble gases are inert, because
their atoms have a stable electronic configuration in which they have eight electrons in the outer shell except
helium which has two electrons. In chemical bonding, only valence electrons (electrons located in
the orbitals of the outermost energy level) of an element, are involved. The core electrons (electrons in filled
shells) do not participate in chemical bonding. Carbon, for example, with the ground-state electronic
configuration 1s2 2s2 2p2, has four outer-shell or valence electrons and two core electrons.
Dr. O. Erharuyi

Figure 2: A pictorial representation of bonds between atoms (The ball and stick model)
For the purpose of explaining chemical bonding, the Lewis electron dot diagram is a model that is generally
used.

Lewis electron dot diagram

Lewis electron dot diagram (or electron dot diagram or a Lewis diagram or a Lewis structure) is a
representation of an atom and its valence electrons. In a Lewis diagram of an element, the symbol of the
element is written in the center and the valence electrons are drawn around it as dots. Lewis structures
provide information about how atoms are bonded to each other, and the total electron pairs involved.
According to the Lewis theory, an atom will give up, accept or share electrons in order to achieve a filled
outer shell that contains eight electrons. Except for hydrogen and helium which filled outer shell contain two
electrons. This stable configuration of electrons is called an octet. Lewis structures help us to track the
valence electrons and predict the types of bond. The number of valence electrons determines the number of
electrons needed to complete the octet of eight electrons. However, not all compounds follow the octet rule.
The total number of electrons in the valence shell of each atom can be determined from its group number in
the periodic table. For example, Sodium (Na) in Group 1A has one valence electron, carbon (C) in Group 4A
has four valence electrons, and chlorine (Cl) in Group 7A has seven valence electrons. An atom having a
filled valence shell is said to have a closed shell configuration.

Na Cl

Figure 3: Lewis dot diagram of sodium and chlorine atoms

Lewis structures are useful as they show what atoms are bonded together, and whether any atoms possess
lone pairs of electrons or have a formal charge.
Dr. O. Erharuyi

Types of chemical bonding

There are two main types (ionic and covalent) and some secondary types of chemical bonds:
Ionic bonds
Ionic bonds result from the transfer of one or more electrons between atoms, so one atom gains an electron
while the other atom loses an electron. An atom that gains electrons becomes an anion, a negatively charged
ion, and an atom that loses electrons becomes a cation, a positively charged ion. Because opposite charges
attract, the atoms bond together to form a molecule. Ionic compounds are held together by the attraction of
opposite charges. Thus, ionic bonds consist of the electrostatic attraction between positively and negatively
charged ions. Ionic bonds are commonly formed between reactive metals, electropositive elements (on the
left hand side of the periodic table), and nonmetals, electronegative elements (on the right hand side of the
periodic table).
For example, Na (electronegativity 0.9) easily gives up an electron, and Cl (electronegativity 3.0) readily
accepts an electron to form an ionic bond. In the formation of ionic compound Na+Cl- the single 3s valence
electron of Na is transferred to the partially filled valence shell of chlorine. When Na+ and Cl– ions combine
to produce NaCl, an electron from a sodium atom stays with the other seven from the chlorine atom, and the
sodium and chloride ions attract each other in a lattice of ions with a net zero charge (Figure 4).

Figure 4: Formation of an ionic compound NaCl

The arrow indicates the transfer of the electron from sodium to chlorine to form the sodium metal ion (Na+)
and the chloride ion (Cl-). Each ion now has an octet of electrons in its valence shell.
Na+: 2s22p6
Cl-: 3s23p6
Dr. O. Erharuyi

Covalent bonds

Covalent bonds result from the sharing of electrons between atoms. The pair of shared electrons forms a new
orbit that extends around the nuclei of both atoms. Elements in organic compounds are joined by covalent
bonds, a sharing of electrons, and each element contributes one electron to the bond.
The shared electrons are called the bonding electrons and may be represented by a line or lines between two
atoms. The valence electrons that are not being shared are the nonbonding electrons or lone pair electrons,
and they are shown in the Lewis structure by dots around the symbol of the atom.

Figure 5: Formation of covalent bond between two atoms

In neutral organic compounds, C forms four bonds, N forms three bonds (and a lone pair), O forms two
bonds (and two lone pairs) and H forms one bond.

The number of electrons necessary to complete the octet determines the number of electrons that must be
contributed and shared by a different element in a bond. This analysis determines the number of bonds that
each element may enter into with other elements. On the basis of the number of electrons that is shared,
covalent bonds can be can be categorized into single covalent bond, double covalent bond and triple
covalent bond. The shared pair is represented as a pair of dots or a line.

In a single bond, two atoms share one pair of electrons and form a sigma bond. Examples: H2, Cl2, Br2, I2, HCl,
NH3, CH4, and C2H6
Dr. O. Erharuyi

H H
Figure 6: Single covalent bond in hydrogen molecule
In a double bond they share two pairs of electrons and form a sigma bond and a pii bond. Examples: O2, CO2,
SO2, and C2H4

Figure 7: Double covalent bond in carbon dioxide molecule

In a triple bond two atoms share three pairs of electrons and form a sigma bond and two pii bonds.
Examples: N2, C2H2, and CN-

Figure 8: Triple covalent bond in carbon nitrogen molecule

Electronegativity and chemical bonding (Nonpolar and polar covalent bonds)

Electronegativity is the ability of an atom that is bonded to another atom or atoms to attract electrons strongly
towards it. This competition for electron density is scaled by electronegativity values. Elements with higher
electronegativity values have greater attraction for bonding electrons. Thus, the electronegativity of an atom
is related to bond polarity. The difference in electronegativity between two atoms can be used to measure the
polarity of the bonding between them. The greater the difference in electronegativity between the bonded
atoms, the greater is the polarity of the bond. If the difference is great enough, electrons are transferred from
the less electronegative atom to the more electronegative atom, hence an ionic bond is formed. In general,
most bonds within organic molecules, including various drug molecules, are covalent. The exceptions are
compounds that possess metal atoms, where the metal atoms should be treated as ions. If a bond is covalent,
it is possible to identify whether it is a polar or nonpolar bond.
Dr. O. Erharuyi

Polar covalent bond

Bonds between different atoms usually result in the electrons being attracted to one atom more strongly than
the other. The more electronegative atom will have greater attraction for the bonding electrons than the less
electronegative atom. This results in a small partial positive charge on the less electronegative atom, and an
equal but opposite partial negative charge on the more electronegative atom. Such an unequal sharing of the
pair of bonding electrons results in a polar covalent bond. The separation of the partial charges creates a
dipole. The word dipole means two poles, the separated partial positive and negative charges. Bond polarity
is measured by dipole moment. The dipole moment is measured in a unit called the debye (D). A polar
molecule results when a molecule contains polar bonds in an unsymmetrical arrangement.
Some examples of polar covalent compounds include; chloromethane (CH3Cl), water (H2O), chloroform
(CHCl3), methanol (CH3OH), hydrogen fluoride (HF), hydrogen chloride (HCl), and ammonia (NH3).
The unequal sharing of electrons can be depicted by a polar arrow. The head of the arrow points to the more
electronegative element. A polar bond can also be marked using δ+ and δ- symbols (Figure 9).
δ-
δ+
OR

Figure 9: Polar bonds in hydrogen fluoride and water molecules

Nonpolar covalent bond

In a nonpolar covalent bond, the electrons are shared equally between two atoms, e.g. H2, F2, O2, N2, and
CH4.
Only if the two atoms have exactly the same electronegativity is a nonpolar bond formed. Nonpolar
molecules whose atoms have equal or nearly equal electronegativities have zero or very small dipole
moments, as do molecules that have polar bonds but the molecular geometry is symmetrical, allowing the
bond dipoles to cancel each other.
Dr. O. Erharuyi

Figure 10: Nonpolar bond in fluorine molecule

In general, if the electronegativity difference is equal to or less than 0.5 the bond is nonpolar covalent, and if
the electronegativity difference between bonded atoms is 0.5–1.9 the bond is polar covalent. If the difference
in electronegativity between the two atoms is 2.0 or greater, the bond is ionic.

Bond polarity and intermolecular forces

Bond polarity is a useful concept for describing the sharing of electrons between atoms. The shared electron
pairs between two atoms are not necessarily shared equally and this leads to a bond polarity. Atoms, such as
nitrogen, oxygen and halogens that are more electronegative than carbon have a tendency to have partial
negative charges. Atoms such as carbon and hydrogen have a tendency to be more neutral or have partial
positive charges. Thus, bond polarity arises from the difference in electronegativities of two atoms
participating in the bond formation. This also depends on the attraction forces between molecules, and these
interactions are called intermolecular interactions or forces. The physical properties, e.g. boiling points,
melting points and solubilities of the molecules are determined, to a large extent, by intermolecular
nonbonding interactions. There are three types of nonbonding intermolecular interaction: Dipole–dipole
interactions, van der Waals forces and hydrogen bonding. These interactions increase significantly as the
molecular weights increase, and also increase with increasing polarity of the molecules.

1. Dipole–dipole interactions

The interactions between the positive end of one dipole and the negative end of another dipole are called
dipole–dipole interactions. As a result of dipole–dipole interactions, polar molecules are held together more
strongly than nonpolar molecules. Dipole–dipole interactions arise when electrons are not equally shared in
the covalent bonds because of the difference in electronegativity. For example, hydrogen fluoride has a
dipole moment of 1.98 D, which lies along the H-F bond. As the fluorine atom has greater electronegativity
than the hydrogen atom, the electrons are pulled towards fluorine, as shown below.
Dr. O. Erharuyi
2. van der Waals forces

Relatively weak forces of attraction that exist between nonpolar molecules are called van der Waals forces or
London dispersion forces. Dispersion forces between molecules are much weaker than the covalent bonds
within molecules. Electrons move continuously within bonds and molecules, so at any time one side of the
molecule can have more electron density than the other side, which gives rise to a temporary dipole. Because
the dipoles in the molecules are induced, the interactions between the molecules are also called induced
dipole–induced dipole interactions. van der Waals forces are the weakest of all the intermolecular
interactions.

Alkanes are nonpolar molecules, because the electronegativities of carbon and hydrogen are similar.
Consequently, there are no significant partial charges on any of the atoms in an alkane. Therefore, the size of
the van der Waals forces that hold alkane molecules together depends on the area of contact between the
molecules. The greater the area of contact, the stronger is the van der Waals forces, and the greater is the
amount of energy required to overcome these forces.

3. Hydrogen bonding

Hydrogen bonding is the attractive force between the hydrogen attached to an electronegative atom of one
molecule and an electronegative atom of the same (intramolecular) or a different molecule (intermolecular).
It is an unusually strong force of attraction between highly polar molecules in which hydrogen is covalently
bonded to nitrogen, oxygen or fluorine. Therefore, a hydrogen bond is a special type of interaction between
atoms. A hydrogen bond is formed whenever a polar covalent bond involving a hydrogen atom is in close
proximity to an electronegative atom such as O or N. The attractive forces of hydrogen bonding are usually
indicated by a dashed line rather than the solid line used for a covalent bond. For example, water molecules
form intermolecular hydrogen bonding.

Figure 11: Hydrogen bonding in water molecule

Dr. O. Erharuyi
Water is a polar molecule due to the electronegativity difference between hydrogen and oxygen atoms. The
polarity of the water molecule with the attraction of the positive and negative partial charges is the basis for
the hydrogen bonding. Hydrogen bonding is responsible for certain characteristics of water, e.g. surface
tension, viscosity and vapour pressure. The intermolecular hydrogen bonding in water is responsible for the
unexpectedly high boiling point of water (b.p. 100

Hydrogen bonds are interactions between molecules and should not be confused with covalent bonds to
hydrogen within a molecule. Hydrogen bonding is usually stronger than normal dipole forces between
molecules, but not as strong as normal ionic or covalent bonds.

Coordinate Covalent Bond or Dative Covalent Bond

In this type of covalent bond, the shared pair of electrons comes from one of the atoms. This kind of bond is
typically observed in the bonding of metal ions to ligands. The atoms are held together because both of the
nuclei attract the electron pair.

Figure 12: Formation of coordinate covalent bond between two atoms

Examples of coordinate covalent compounds are NH4+, BF3.NH3, H3O+, Al2Cl6, HNO3, and CO
1. Ammonium (NH4+) ion
The ammonium ion is formed from the reaction of ammonia (NH3) gas with hydrogen chloride (HCl) gas. In
NH4+, the fourth hydrogen is attached by a coordinate covalent bond because only the hydrogen’s nucleus is
transferred from the chlorine to the nitrogen. The hydrogen’s electron is left behind on the chlorine to form a
negative chloride (Cl–) ion.
Dr. O. Erharuyi
2. Ammonia Boron Trifluoride (NH3.BF3)
Boron trifluoride (BF3) is a compound that does not have a noble gas structure around the boron (B) atom.
The boron only has three pairs of electrons in its valance shell and requires a pair to complete the
orbital. Hence, BF3 is electron deficient. The lone pair on the nitrogen (N) of the ammonia (NH3) molecule
is used to overcome that deficiency, and a complex compound forms through a coordinate covalent bond.

3. Hydronium ion (H3O+)

When hydrogen chloride (HCl) gas dissolves in water to make hydrochloric acid (HCl aq.), a coordinate
covalent bond is formed in the hydronium ion. The hydrogen (H) nucleus is transferred to the water (H2O)
molecule, which has a lone pair of electrons to form hydronium. So, H does not contribute any electrons to
the bond.

4. Aluminum Chloride (Al2Cl6)

The bonding in aluminum chloride (AlCl3) is essentially covalent. Each aluminum (Al) atom has a deficit of
two electrons in its valance shell, and chlorine (Cl) has a lone pair. Al forms a coordinate covalent bond with
the Cl atom on an adjacent AlCl3 group. As each of two Al atoms does this, then aluminum chloride is a
covalent dimer molecule with the formula Al2Cl6.

5. Carbon monoxide (CO)

Carbon (C) has four electrons in its valence shell, and oxygen (O) has six. Both carbon and oxygen share
their two electrons. While the octet rule is satisfied with oxygen, there is still a deficit of two electrons on the
carbon. So, oxygen shares its two electrons with carbon to form a coordinate covalent bond, in addition to the
two regular (double) covalent bonds.
Dr. O. Erharuyi

Importance of Chemical bonding in Pharmacy and Medicine

 The hydrogen bond is of fundamental importance in biology. The hydrogen bond is said to be the
‘bond of life’. The double helix structure of DNA is formed and held together by hydrogen bonds.
 Hydrogen bonds are also responsible for some of the three-dimensional structure of proteins. The
nature of the hydrogen bonds in proteins dictates their properties and behaviour. Intramolecular
hydrogen bonds (within the molecule) in proteins result in the formation of globular proteins, e.g.
enzymes or hormones. On the other hand, intermolecular hydrogen bonds (between different
molecules) tend to give insoluble proteins such as fibrous protein.
 Cellulose, a polysaccharide, molecules are held together through hydrogen bonding, which provides
plants with rigidity and protection.
 In drug–receptor binding, hydrogen bonding often plays an important role. Most drugs interact with
receptor sites localized in macromolecules that have protein-like properties and specific three-
dimensional shapes. A receptor is the specific chemical constituents of the cell with which a drug
interacts to produce its pharmacological effects. The drug–receptor interaction, i.e. the binding of a
drug molecule to its receptor, is governed by various types of chemical bonding. A variety of
chemical forces may result in a temporary binding of the drug to its receptor. Interaction takes place
by utilizing the same bonding forces as involved when simple molecules interact, e.g. covalent (40–
140 kcal/mol), ionic (10 kcal/mol), ion–dipole (1–7 kcal/mol), dipole–dipole (1–7 kcal/mol), van der
Waals (0.5–1 kcal/mol), hydrogen bonding (1–7 kcal/ mol) and hydrophobic interactions (1
kcal/mol). However, most useful drugs bind through the use of multiple weak bonds (ionic and
weaker). Covalent bonds are strong, and practically irreversible. Since the drug–receptor interaction is
a reversible process, covalent bond formation is rather rare except in a few situations.

References
Chemistry for Pharmacy Students, General, organic and Natural products Chemistry (Satyajit D.
Sarker and Lutfun Nahar), 2nd Edition, 2019. John Wiley & Sons Ltd, The Atrium, Southern Gate,
Chichester, West Sussex PO19 8SQ, England

OpenStax, Concepts of Biology. OpenStax CNX. March 22, 2017. Available from:
https://cnx.org/contents/[email protected]:IBRqRY3C@8/The-Building-Blocks-of-Molecul

Chemistry LibreTexts.
Available from: https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_Chem_400_-
_General_Chemistry_I/Text/09%3A_Chemical_Bonding_I%3A_Drawing_Lewis_Structures/9.02%3A_Type
s_of_Chemical_Bonds