Chemistry of Materials Lecture 4

Chemistry of Materials
TMS 1122
Faculty of Technology, University of Ruhuna
Mrs. D.N. Liyanage

Department of Engineering Technology
1
Learning Objectives of Lecture
At the end of the lecture you will able to

Define the Electronegativity , Electronegativity and bond types
Explain types of Chemical bonding Fajans rule
Understand polarity of diatomic molecules and Dipolar moment
Intermolecular forces Metallic bonding
Differentiate Melting point & Boiling point
Electronegativity and diatomic molecules
Homonuclear diatomic Heteronuclear diatomic

molecules: molecules:
If the atoms are equally If the atom B is slightly more

electronegative, both have the electronegative, then B will attract
same tendency to attract the the electron pair rather more than A
bonding pair of electrons, and so it does.
will be found on average half way Then the atom B becomes slightly
between the two atoms. negative and A will be slightly
e.g. H2 or Cl2 molecules. positive.
e.g. HCl, HBr molecules.
Electronegativity and Bond Types
The difference in the electronegativity of two elements chemically joined in a compound
determines the nature of the bond between them :
if a bond is to be classified as
- nonpolar-covalent : e.g. Cl2
- polar-covalent : e.g. HCl
- Ionic : e.g. Nacl
Electronegativity and Bond Types
If the electronegativity difference (usually called EN) is
less than 0.5 ➔ the bond is nonpolar-covalent
between 0.5 -1.6➔ the bond is polar covalent
more than 2.0 ➔ the bond is ionic
If the EN is between 1.6 - 2.0 and

if a metal is involved, then the bond is considered as ionic
if only nonmetals are involved, the bond is considered as polar-

covalent
Types of Chemical Bonding
Chemical compounds are formed by the joining of two or more atoms. A
stable compound occurs when the total energy of the combination has lower
energy than the separated atoms.
Ionic bond:
Bond in which one or more electrons from one atom are removed and attached to another
atom, resulting in positive and negative ions which attract each other.
Ionic bonds do not hold molecules together by sharing electrons;- they hold them
together because of the electrostatic attraction between the two oppositely charged ions.
The oppositely charged and ions that result when sodium transfers an electron to chlorine are
attracted to one another by electrostatic forces, and we say that they are joined by an ionic bond.
The crystalline substance that results is said to be an ionic solid .
• Covalent bond:
• Bond in which one or more pairs of electrons are shared by two atoms.
• E.g :
H–H bond in the molecule as an example. As two hydrogen atoms come
closer together, electrostatic interactions begin to develop between them.
The two positively charged nuclei repel each other and the two negatively
charged electrons repel each other, but each nucleus attracts both electrons.
If the attractive forces are stronger than the repulsive forces, a
covalent bond is formed, with the two atoms joined together and the two shared
electrons occupying the region between the nuclei.
Fajan’s Rule
Fajans' Rules, formulated by Kasimir Fajans, are used to predict whether
a chemical bond will be covalent or ionic, and depend on the charge on
the cation and the relative sizes of the cation and anion. They can be
summarized in the following table:
Ionic Covalent
Low positive charge High positive charge
Large cation(>~100pm ) Small cation (<~100 pm )
Small anion Large anion

Polarization
Although the bond in a compound like X+Y- may be considered to be 100% ionic, it
will always have some degree of covalent character. When two oppositely charged
ions (X+and Y-) approach each other, the cation attracts electrons in the outermost
shell of the anion but repels the positively charged nucleus.
This results in a distortion, deformation or polarization of the symmetrical shape

of the electron cloud of anion. If the degree of polarization is quite small, an ionic
bond is formed, while if the degree of polarization is large, a covalent bond results.
Polarizing power & Polarizability
The ability of a cation to distort an anion is known as its polarization power.
The tendency of the anion to become polarized by the cation is known as its
polarizability.
The polarizing power and polarizability that enhances the formation of

covalent bonds.
e.g. LiI
Li+ is small. It has the power to polarize electron cloud of I- ion.
I- ion is large. It has the ability to be polarized
Therefore, LiI shows some covalent properties.

Factors affecting Polarizing power of cation
-Magnitude of the positive charge of the cation when +ve charge
increases polarizing power increases; e.g. Na+ < Mg2+ < Al3+
- Size of the cation
When size decreases attraction of outermost electron increases
then polarizing power increases; e.g. Li+ > Na+ >K+
-Electron configuration of the cation
When same charge and same size then polarizing power change with
the electron configuration;
e.g. polarizing power: ns2 np6 nd10 > ns2 np6
The reason is d- electrons have poor shielding power.
Factors affecting Polarizability of anion
-Magnitude of the negative charge of the anion

when -ve charge increases ➔ polarizability increases
e.g. C4- > N3- <O2-
- Size of the anion
When size increases polarizability increases
e.g. F- < Cl- < Br- <I-
Other Types of Chemical Bonding
Other types of bonds include coordinate bond, metallic bonds and hydrogen
bonding. The attractive forces between molecules in a liquid can be
characterized as van der Waals bonds.
Coordinate bond/ dative covalent bond

A co-ordinate bond is a covalent bond (a shared pair of electrons) in which both
electrons come from one atom (donor atom). This can happen if the donor atom
has a non-bonding pair of electrons and the acceptor atom has a completely
empty orbital that can accommodate them.
Dipole Moment
A dipole moment arises in any system in which there is a separation of charge. They
can, therefore, arise in ionic bonds as well as in covalent bonds. Dipole moments
occur due to the difference in electronegativity between two chemically bonded
atoms.
A bond dipole moment is a measure of the polarity of a chemical bond between two
atoms in a molecule.
The bond dipole moment is a vector quantity. it has both magnitude and direction.
Bond Dipole Moment Formula μ = 𝛿.d
Where: μ is the bond dipole moment,

𝛿 is the magnitude of the partial charges 𝛿+ and 𝛿–,
And d is the distance between 𝛿+ and 𝛿–.
• Polar molecules have uneven distribution of charges.
• Examples: BeF2 the net dipole moment of a BeF2 molecule is
zero.
• In a water molecule, the electrons are localized around the
oxygen atom since it is much more electronegative than the
hydrogen atom. Presence of a lone pair of electrons in the
oxygen atom causes the water molecule to have a bent shape.
The individual bond dipole moments do not cancel each other
out.
Dipole Moment: Nonpolar and Polar Molecules
Polar molecules have a dipolar moment (µ ≠ 0)

Nonpolar molecules have zero dipolar moment (µ = 0)
Intermolecular Forces
Hydrogen Bond:
A hydrogen bond is the electrostatic attraction between two polar groups that
occurs between a H atom, covalently bound to a highly electronegative atom such
as N, O or F, with another highly electronegative atom nearby.
This type of bond always involves a hydrogen atom, thus the name - Hydrogen
Bonding.
These bonds can occur between molecules (inter-molecularly), or within different

parts of a single molecule (intra-molecularly).
The hydrogen bond is a very strong fixed dipole-dipole van der Waals force, but
weaker than covalent, ionic and metallic bonds.
• The partially positive end of hydrogen is attracted to the partially negative
end of the oxygen, nitrogen, or fluorine of another molecule.
• Hydrogen bonding is a relatively strong force of attraction between
molecules, and considerable energy is required to break hydrogen bonds.
Dipole-dipole force: interaction between two polar molecules (that have permanent
dipole moments)
These forces occur when the partially positively charged part of a molecule interacts
with the partially negatively charged part of the neighboring molecule.
Dipole-dipole interactions are the strongest intermolecular force of attraction.
e.g. HCl and CH3-Cl
Dipole-Induced Dipole Forces
This occurs between polar and Non-polar molecules,
e.g. a mixture of HCl with Ar
The electrons on an Ar atom are distributed homogeneously around the nucleus of
the atom. But these electrons are in constant motion. When an Ar atom comes close
to a polar HCl molecule, the electrons can shift to one side of the nucleus to produce
a very small dipole moment that lasts for only an instant.
This creates a weak dipole-induced dipole force of attraction between the HCl
molecule and the Ar atom.
London dispersion force interaction between temporary induced dipoles.
These are the weakest of the intermolecular forces and exist between all types of
molecules, whether ionic or covalent—polar or nonpolar.
Also, the breaking of London dispersion forces doesn’t require that much energy.
Metallic bonding
Metallic bonding is the force of attraction between valence electrons and the metal ions.
Metallic bonds are formed between two or more metal cations.
It is the sharing of many detached electrons between many positive ions, where the
electrons act as a "glue" giving the substance a definite structure. It is unlike covalent or
ionic bonding.
Metal atoms release their valence electrons into a sea of valence electrons shared by all
metal atoms. The attraction of these free electrons to the metal cations is called a
metallic bond.
Melting point & Boiling point
Melting point: The melting point of a solid is the temperature at which it changes
state from solid to liquid at atmospheric pressure. MP depends on pressure and is
usually specified
at standard pressure.
When considered as the temperature of the reverse change from liquid to solid, it
is referred to as the freezing point.
Melting points are often used to help identify compounds.
Measurements of the melting point of a solid can also provide information about the
purity of the substance. Pure, crystalline solids melt over a very narrow range of
temperatures, whereas mixtures melt over a broad temperature range.
Mixtures tend to melt at temperatures below the melting points of the pure solids.
Melting point & Boiling point
Boiling point: The boiling point of a substance is the temperature at which the
vapor pressure of the liquid equals the pressure surrounding the liquid and the
liquid changes into a vapor.
Once the liquid starts to boil, the temperature remains constant until all of the liquid
has been converted to a gas.
The normal boiling point of water is 100oC. But in mountains at an elevation of
10,000 feet, water boils at only 90oC, and it takes longer time to cook food.
In theory, you shouldn't be able to heat a liquid to temperatures above its normal
boiling point. But in a typical pressure cooker, water can remain a liquid at
temperatures as high as 120 oC, and food cooks in as little as one-third the normal
time.
Melting point & Boiling point of H2O
• Melting and boiling occur at constant temperatures

• The heat supplied at hidden “latent”
• Bonds between molecules are weakened in melting and
broken in boiling
• More energy is required for boiling than melting

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Chemistry of Materials

Mrs. D.N. Liyanage

At the end of the lecture you will able to

Homonuclear diatomic Heteronuclear diatomic

If the atoms are equally If the atom B is slightly more

less than 0.5 ➔ the bond is nonpolar-covalent

between 0.5 -1.6➔ the bond is polar covalent

more than 2.0 ➔ the bond is ionic

If the EN is between 1.6 - 2.0 and

if only nonmetals are involved, the bond is considered as polar-

Low positive charge High positive charge

Large cation(>~100pm ) Small cation (<~100 pm )

Small anion Large anion

This results in a distortion, deformation or polarization of the symmetrical shape

The polarizing power and polarizability that enhances the formation of

Therefore, LiI shows some covalent properties.

-Magnitude of the negative charge of the anion

Coordinate bond/ dative covalent bond

Bond Dipole Moment Formula μ = 𝛿.d

Where: μ is the bond dipole moment,

Polar molecules have a dipolar moment (µ ≠ 0)

These bonds can occur between molecules (inter-molecularly), or within different

• Melting and boiling occur at constant temperatures

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