CHAPTER 2:

BONDING AND PROPERTIES

ISSUES TO ADDRESS...
 WHY Study Atomic Structure and Interatomic Bonding
 Atomic bonding in solids
 Bonding Forces and Energies
 WHY Study Atomic Structure and
Interatomic Bonding
 An important reason to have an understanding of inter-
atomic bonding in solids is that, in some instances, the
type of bond allows us to explain material’s properties.
 For example, consider carbon, which may exist as both
graphite and diamond.
 Graphite is relatively soft and has a ‘‘greasy’’ feel to it.
 Diamond is the hardest known material.
 This dramatic disparity in properties is directly
attributable to a type of inter-atomic bonding found in
graphite that does not exist in diamond.
The type of bond allows us to explain material’s properties, which
significantly affected by………………………of the materials.
 Example: Diamond and Graphite
• Carbon alone forms the familiar substances and diamond.
• Both graphite and diamond are made only of carbon atoms.
• Graphite is very soft and slippery.
• Diamond is the hardest substance known to man.
• If both are made only of carbon what gives them different
properties?

Diamond Graphite
Graphite: While there are
strong covalent bonds between
carbon atoms in each layer, there
are only weak forces between
layers. This allows layers of
carbon to slide over each other
in graphite.
Diamond: Each carbon atom is the
same distance to each of its
neighboring carbon atoms. In this
rigid network atoms cannot move.
This explains why diamonds are so
hard and have such a high melting
point.
 Multiple Choice Questions
Graphite can be described as
a) hard and crystalline
b) soft and slippery
c) a dark liquid
d) made only of carbon and hydrogen atoms
Diamond is
a) made only of carbon and hydrogen atoms
b) the hardest substance know to man
c) soft and slippery
d) clear and brittle
What makes diamond so hard?
a) diamond has a crystal structure similar to ice
b) diamond is made up of only carbon atoms
c) the C-C bonds all have different bond lengths
d) a rigid network of atoms that cannot move
 Multiple Choice Questions
Which statement best describes why graphite is soft?
a) graphite is made up of only carbon atoms
b) graphite is layered
c) graphite has a low melting point
d) none of the above
Which of the following statements is not correct
a) both carbon and diamond are made of only carbon atoms
b) graphite has only weak forces between its layers
c) graphite and diamond have the same density
d) in diamond each carbon is the same distance to each of its neighboring
carbon atoms
 Primary Bonding: IONIC BONDING
• Ionic bonding is always found in compounds that are composed
of both metallic and nonmetallic elements
• It is a predominant bonding in Ceramics

NaCl
MgO
H He
2.1 CaF 2 -
Li Be O F Ne
1.0 1.5 Cs Cl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

 Properties of ionic compounds
Ionic compound Properties
Thermal: High melting point: 800ºC
Sodium chloride, Electrical: Non-conductive in its solid
NaCl state, but when dissolved in water or
molten, NaCl will conduct electricity.
Thermal: Higher melting point than
sodium chloride: around 2,800ºC.
Electrical: Because magnesium oxide
Magnesium oxide,
stays solid at such high temperatures, it
MgO
remains non-conductive, therefore, is
used for high-temperature electrical
insulation.
Difference in properties due to fact that Mg2+ and O2- ions have
a greater number of charges, so they form stronger ionic bonds
than the Na+ and Cl- ions in sodium chloride.
 COVALENT BONDING
• In covalent bonding, stable electron configurations are
assumed by the sharing of electrons between adjacent
atoms.
• Covalent form between non-metal atoms and
• Also found in elemental solids such as diamond (carbon),
silicon, and germanium and other solid compounds
composed of elements that are located on the right-hand
side of the periodic table.
• Each bond consists of a shared pair of electrons, and is
very strong.
• Covalently bonded substances fall into two main types
1. Simple molecules and
2. Giant covalent structures.
 Simple molecules
A molecule of carbon dioxide
These contain only a few atoms held together by strong covalent
bonds. An example is carbon dioxide (CO2), the molecules of which
contain one atom of carbon bonded with two atoms of oxygen.

Properties of simple molecular substances

1. Low melting and boiling points - This is because the weak
intermolecular forces break down easily.
2. Non-conductive - Substances with a simple molecular structure
do not conduct electricity. This is because they do not have any
free electrons or an overall electric charge.
 EXAMPLES: COVALENT BONDING
H2 O

column IVA
H2 F2
C(diamond)
H He
2.1
Si C - Cl 2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA)
 Giant Molecules
 Giant covalent structures contain a lot of non-metal atoms, each
joined to adjacent atoms by covalent bonds.
 The atoms are usually arranged into giant regular lattices -
extremely strong structures because of the many bonds
involved.
 The graphics show the molecular structure of diamond and
graphite: two allotropes of carbon, and of silica (silicon dioxide).
 Properties of giant covalent structures
• Very high melting points
– Substances with giant covalent structures have very
high melting points, because a lot of strong covalent
bonds must be broken.
– Graphite and diamond, for example, have melting
points of more than 3,600ºC.
• Variable conductivity–
– Diamond does not conduct electricity.
– Graphite contains free electrons, so it does conduct
electricity.
– Silicon is semi-conductive - that is, midway between
non-conductive and conductive.
 Metallic bonding - higher
• Metallic bonding is found in metals and their alloys.
• It forms giant structures with free electrons.
• Metals form giant structures in which electrons in the outer
shells of the metal atoms are free to move.
• The metallic bond is the force of attraction between these free
electrons and metal ions.
• Metallic bonds are strong, so metals can maintain a regular
structure and usually have high melting and boiling points.
• Metals are good conductors of electricity and heat, because the
free electrons carry a charge or heat energy through the metal.
• The free electrons allow metal atoms to slide over each other, so
metals are malleable and ductile.
 METALLIC BONDING
+ + +

+ + +

+ + +
• The free electrons shield the positively charged ion cores from
mutually repulsive electrostatic forces.
• These free electrons act as a “glue” to hold the ion cores
together.
• In general, metallic bonding is found in the periodic table for
Group IA and IIA elements and, in fact, for all elemental
metals.
 SECONDARY BONDING: Van der Waals bonding
• Weak bonds in comparison with other forms of bonding (~10
kJ/mol)
• Evident between all atoms, including inert gases and especially
between covalently bonded molecules (i.e. Graphite).
• Bonds are created through both atomic and molecular dipoles.
Secondary Bonding: Hydrogen bonding
• Special type of secondary bond between molecules with
permanent dipoles and hydrogen in the compound. Ex: HF, H2O,
NH3
• These secondary bonds can have strengths as high as ~50 kJ/mol
and will cause increases in melting temperature above those
normally expected.
Bonding Energies and Melting Temperatures for Various
Substances
 General Characteristics of Substances with different
Interatomic Bonding
 MID TERM 1

Date: Thursday, October 30/ 2014

Time: TBD (after 2:00pm)
Venue: TBD
BONDING FORCES AND ENERGIES
 Molecular Mechanics
 Non-bonded atoms (greater
than two bonds apart)
interact through van der
Waals attraction
 These properties are easiest
to describe mathematically
when atoms are considered
as spheres of characteristic
radii.
Energy =Stretching Energy
+Bending Energy The mathematics of spring
+Torsion Energy deformation can be used to
+Non-Bonded describe the ability of bonds to
Interaction Energy stretch, bend, and twist.
 BONDING FORCES AND ENERGIES
 The principles of atomic bonding are best illustrated by
considering the interaction between two isolated atoms as they
are brought into close proximity from an infinite separation.
 At large distances, the interactions are negligible, but as the
atoms approach, each atom exerts forces on the other.
 These forces are of two types, attractive (FA) and repulsive
(FR) , and the magnitude of each is a function of the separation
or interatomic distance.
 The net force FN between the two atoms is just the sum of both
attractive and repulsive components; that is
FN = FA + FR
 Then a state of equilibrium exists, when FN =0
 Columbic force
 The attractive bonding forces are columbic; that is, positive
and negative ions, by virtue of their net electrical charge,
attract one another.
 For two isolated ions, the attractive energy EA is a function of
the interatomic distance according to
A
EA = 
r
 An analogous equation for the repulsive energy is
B
ER = n
r
 A, B, and n are constants whose values depend on the
particular ionic system. The value of n is approximately 8.
 Farad and Permittivity
 The Farad (symbol: F) is the SI unit of capacitance.
 Capacitance is the ability of a body to store an electrical
charge.
 It is named after the British physicist Michael Faraday.
 Work-done or energy can be measured in Joules and
charge is measured in Coulombs so the electrical
potential (V) can be measured in Joules per Coulomb
which has been defined as a volt.
Values of Selected Physical Constants
 Columbic force
A
 The constant A in Equation E A =  is
r
Farads per meter
 0 is the permittivity of a vacuum 8.85×10-12 F/m,
 Permittivity is the measure of the resistance that is encountered
when forming an electric field in a medium.
 Z1 and Z2 are the valences of the two ion types,
 e is the electronic charge
 Sometimes bonding energies are expressed per atom or per ion.
Under these circumstances the electron volt (eV) is a conveniently
small unit of energy.
 It is, by definition, the energy imparted to an electron as it falls
through an electric potential of one volt.
BONDING FORCES AND ENERGIES
BONDING FORCES AND ENERGIES

E0 = represents the minimum energy that would be

required to separate these two atoms to an infinite
separation.
 BONDING FORCES AND ENERGIES
The magnitude of the attractive
force varies with the distance, as
represented schematically.
The net curve has a potential
energy trough or well around its
minimum.

The bonding energy for these

two atoms, E0, corresponds to
the energy at this minimum
point.
It represents the energy that
would be required to separate
these two atoms to an infinite
separation.
Example-1
Calculate the force of attraction between a Ca2+ and an O2- ion the
centers of which are separated by a distance of 1.25 nm.
Take attractive energy and the material constant A as
A
A
Z1e  Z 2 e 
EA = 
r 4πεo

Given:
Z1 =2=Z2
R=1.25nm
e= 1.602×10-19 C
Example-1: Solution
Calculate the force of attraction between a Ca2+ and an O2- ion the
centers of which are separated by a distance of 1.25 nm.
Take attractive energy as
A  A
EA =  d  
r dE A  r A
FA = = = 2
dr dr r
Given: A
Z1e  Z 2 e 
Z1 =2=Z2 4πεo
R=1.25nm
e= 1.602×10-19 C
(2)( 2)1.602 x 10 19 C 
2

FA =  = 5.89  10 -10 N
(4)( ) 8.85 x 10 F / m) 1.25 x 10 m 
12 9 2
Example 2
The net potential energy between two adjacent ions, may be
represented by A B
E N = -  (n )
r r
Calculate the bonding energy in terms of the parameters A, B,
and n using the following procedure:
1. Differentiate EN with respect to r, and then set the
resulting expression equal to zero, since the curve of
versus r is a minimum at E0.
2. Solve for r in terms of A, B, and n, which yields r0 , the
equilibrium interionic spacing.
3. Determine the expression for E0 by substitution of r0 into
given Equation (i.e. EN)
 Example 2: Solution
1. Differentiation of (EN) Equation gives:
dE N A nB
= (1 + 1)  (n + 1) = 0
dr r r
2. Now, solving for r (= r0)
1/(1- n)
A nB  A
2
= (n + 1)  ro =  
ro ro  nB 

3. Substitution for r0 into EN Equation and solving for E (= E0)

A B
Eo =  + n 
ro ro
A B
= 1/(1- n)
+ n/(1 - n)
 A  A
   
 nB   nB 
Class activity Problem
The bonding energy curve for secondary bonding is

Calculate
• FA
• FR
• r0
• E0
 RELATIONSHIP BETWEEN
BONDING ENERGY AND Materials
PROPERTIES
• Stiffness (E)
• Thermal Coefficient ()
 PROPERTIES FROM BONDING: E
• Elastic modulus, E cross
sectional
length, Lo
area A o Elastic modulus
undeformed
L F DL
=E
Ao Lo
deformed F

• E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus

 PROPERTIES FROM BONDING: 
• Coefficient of thermal expansion, a
length, Lo Coefficient of thermal expansion
unheated, T 1
L DL
= a (T2 -T1 )
heated, T 2 Lo

Energy

ro
r a is larger if Eo is smaller.
larger 

small er 
Class Activity Problem
Draw the dependence of net energy (i.e. Potential Energy) on
interatomic separation for Material with
1. High strength
2. Moderate strength
3. Low strength
 Conclusions
• The magnitude of the attractive force varies with the
inter-atomic distance.
• The net bonding energy influences the process, structure,
materials properties and performance. Accordingly,
• As E0 increases, the strength of the material increases.
• As E0 increases, the stiffness of the material increases.
• As E0 increases, the melting point of the material
increases.
 What about
• Hardness
• Softness
• Compliance (inverse of stiffness)
• Toughness (i.e. the ability of a material to absorb energy and
plastically deform before fracturing)
• Abrasion/wear (A hard and wear-resistant material (commonly
a ceramic) that is used to wear, grind, or cut away other
material)
• Malleability (Malleability is a material's ability to deform
under pressure (compressive stress)
• Drilling.
Which properties from above are affected by van der wall?