ATOMIC AND IONIC

BONDING
ATOMIC BONDING
• There are two main types of chemical
bonds
• Primary bonds and Secondary bonds
• Primary bonds are further divided into
three classes
• Ionic bonds
• Covalent bonds
• Metallic bonds
2
SECONDARY BONDS
• These are not as strong as primary bonds and
are divided into
• Permanent Dipole bonds
• Fluctuating dipole bonds

3
 ATOMIC BONDING IN SOLIDS

IONIC BONDING

• Occurs between +
Requires
and
• - ions.electron
• Large difference in electronegativity required.
transfer.
• Example: NaCl
Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable 8

Attraction
 Atomic Bonding in solids – Types of
Bonding
• Predominant bonding in Ceramics
EXAMPLES: IONIC NaCl
BONDING MgO
H He
2.1 CaF 2 -
Li Be O F Ne
1.0 1.5 CsCl 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
9

Give up Acquire electrons

 IONIC BONDING
• An electropositive element and an
electronegative element exchange one or
more electrons to create ions
• Ionic bonding forces are due to electrostatic
forces of attraction of oppositely charged ions
• Two oppositely charged particles will attract
each other if they approach each other from
a large distance
• Eventually their electron charge clouds will
interact and repulsive forces will arise
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Atomic Bonding in solids – Forces &
Energies

Dependence of repulsive, attractive, and

net forces on interatomic separation for
IONIC BONDING
• The net force is equal to the sum of
the attractive and repulsive forces
• If the net force is zero the ions will
remain at an equilibrium distance
• This equilibrium distance is called the
interionic distance a0.

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Fnet Fattractive  Frepulsive

Fattractive 
z1e z 2 e   2
z1 z 2 e
4 0 a 2
4 0 a 2

nb
Frepulsive  n 1
a
2
z1 z 2 e nb
Fnet   n 1
4 0 a 2
a

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• z1z2 are the numbers of electrons
removed or added from the atoms
• e is the electron charge 1.6 x 10-19c
• a is the interionic separation distance
• 0 is the permitivity of free space
8.85 x 10-12 [c2/Nm2]
• n and b are constants

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Ionic bonding energy point of
view
• Chemical bonding occurs due to a net decrease in
potential energy of the atoms in the bonded state
• Assume there are only attractive forces
• The net energy of the system decreases if we
reduce the interionic distance
• A decrease in interionic distance means a
decrease in potential energy
• Since potential energy is set at zero for an infinite
interionic distance, the potential energy due to
the attractive forces at any distance is negative
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Atomic Bonding in solids – Forces &
Energies

Dependence of repulsive, attractive, and

net potential energies on interatomic
Ionic bonding
• Assume there are only repulsive forces
• If the interionic distance is decreased,
work is exerted or the energy of the
system is increased
• If the potential energy is zero for an
infinite interionic distance, the potential
energy for any other distance is positive

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• Bonding exists because the system strives
after a minimum potential energy.
• Thus the sum of the potential energy due to
both attraction and repulsion must be at a
minimum
• It takes energy to separate the ions over an
infinite distance again
• This energy is called bonding energy

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 NET ENERGY

The net energy between a pair of

oppositely charged ions is given by

2
z1 z 2 e b
Enet   n
4 0 a a
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COVALENT BONDING

• Takes place between atoms with small difference

in electronegativity
• Atoms share outer electrons
• Obtain noble gas configuration
• Two types of bonds
• Single covalent bond
• Multiple covalent bond 16
 Atomic Bonding in solids – Types of
Bonding

COVALENT BONDING
shared electrons
H from carbon atom
• Requires shared electrons
CH 4
• Example: CH4
C: has 4 H C H
valence e,
shared electrons
needs 4
H: has 1 valence e, from hydrogen
H
more
needs 1 more
atoms
10

Electronegativities
are comparable.
SINGLE COVALENT BOND
• Each atom contributes one electron to form an
electron pair bond
• Example flourine – flourine

• F-F

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MULTIPLE COVALENT BOND
• Each of the two atoms involved contribute more
than one electron
• Multiple electron pair bonds can be formed by
one atom with itself or other atoms
• O =O N ≡ N

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 Atomic Bonding in solids – Types of
Bonding
H2O EXAMPLES: COVALENT

column IVA
H2 BONDING
F2
C(diamond)
H He
2.1
SiC - 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 11

• Elemental solids (RHS of Periodic Table)

Molecules with metals and nonmetals
• Compound solids (about column IVA)
METALLIC BONDING
• Occurs in solid metals
• Forms relatively close packed solids
• So closely packed that outer valency
electrons attracted by neighbouring
atoms
• Outer electrons can easily jump
• Result in a positive ion core surrounded
by cloud of valency electrons
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METALLIC BONDING
• Electrons can move easily in the cloud
• High thermal and electronic conductivity

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 Atomic Bonding in solids – Types of
Bonding
METALLIC BONDING
• Arises from a sea of donated valence electrons (1,
2, or 3 from each atom).

12

Primary bond for metals and their alloys

 PROBLEM ONE
•
 PROBLEM 2
•
CRYSTAL STRUCTURES

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CRYSTAL STRUCTURE
• Arrangement of ions, atoms or molecules determine the
properties of materials
• Based on structure of atoms, solid materials are classified
into two groups
• Amorphous materials
• Crystalline materials

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AMORPHOUS MATERIALS
• Resemble liquids in their internal arrangements
• Glass is a typical example – described as a super
cooled liquid

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CRYSTALLINE MATERIALS
• Atoms arranged in repeating three dimensional
pattern – crystal structure
• Metals and some ceramic materials are crystalline
• Solids may be single crystal or several crystals -
polycrystalline

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ATOM ARRANGEMENT
• Described by using a space lattice
• Atoms referred as points of intersection
of a network of lines.
• Each point has identical surroundings
• In an ideal crystal the grouping about a
certain lattice point is identical to the
grouping about any other lattice point

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PRINCIPAL CRYSTAL STRUCTURES

• Body centred cubic (BCC)

• Face centred cubic (FCC)
• Hexagonal close packed (HCP)

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EXAMPLES OF CRYSTAL
STRUCTURES

32
BCC
• Has one atom located at the centre
• An eighth of an atom at each corner
• Thus there is an equivalent of two atoms per BCC unit
cell

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FCC
• One atom at each of the face centres
• An eighth of an atom at each corner of the unit cell
• Therefore an FCC unit cell has a total of 4 atoms

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HCP
• Has an atom at each of the two faces
• Has an atom at each of the corners of the hexagon
• Has three atoms at the centre of the unit cell
• Hence an HCP structure has a total of 6 atoms

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ATOMIC PACKING FACTOR
• ATP = Volume of atoms in unit cell
Volume of the unit cell
Example APF for BCC structure
For BCC 4R = a3
Where a is the lattice constant and R is the atomic
radius

So APF = 2*(4/3)**R3 = 2*(4/3)**R3

a3 (4R/3)3

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APF = 2*(4/3)**R3 = 2*(4/3)**R3
a3 (4R/3)3
APF for BCC = 0.68

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EXERCISE
• Show that the APF for an FCC structure is 0.74

• Determine the APF for a simple cubic structure

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ASSIGNMENT
1 Show that the idea c/a ratio for HCP is 1.633
2 Indium has a tetragonal unit cell for which the a and c
lattice parameters are 0.459 nm and 0.495 nm
respectively. If its density, atomic weight and atomic
radius are 7.31 g/cm3, 114.82 g/mol and 0.1625 nm,
respectively, compute the atomic packing factor.
3 Cobalt has an HCP crystal structure, an atomic radius
of 0.1253 nm and a volume of 6.64x10-2 nm3. Compute
the c/a ratio for Cobalt.

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ALLOTROPY
• Elements that exist in more than one crystalline form
are said to exhibit allotropy.
• Examples: Diamond and graphite are allotropic forms
of carbon

• Others are Iron

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