COVALENT BONDING

 A covalent bond is a chemical bond formed by the sharing of

a pair of electrons Between atoms.

 The electrons are attracted simultaneously by the

positive charges of the two hydrogen nuclei.
 This attraction that bonds the electrons to both
nuclei is the force holding the atoms together
 Covalent bond character

Bond order is the number of electrons pairs being shared

between any two bonded atoms. (H2, and HF has one
bond order)
Depending on the number of bond order, molecules have
different types of bonds.

i. Single bond: - this type of bond has only one bond

order (H2. Cl2, F2, HF. )
ii. Double bond: - consists of two bonding pairs (oxygen
gas (O2), CO2, ethane (C2H4))
iii.Triple bond: - consists of three bonding pairs (N2)
 Conti……….Covalent bond character
• bond energy (BE) is the energy required to overcome the
attraction between the bonded nuclei and the shared
electrons.
• bond length, the distance between the nuclei of two
bonded atoms. This bond length is shown as the distance
between the nuclei at the point of minimum energy.
• polar covalent bond-The shared electrons can not be
shared equally between the two atoms. Eg.CH4,CO2…
• Non- polar covalent bond..The shared electrons can be
shared equally between the two atoms. This depends on
the electronegative difference of the two bonded
atoms.Eg.H2,N2,F2,…
General properties of covalent compounds
Because of the weak intermolecular force, covalent compounds
show the following general properties.
• They are often gases and liquids, except few compounds like
quartz and diamond. This is due to the weak attraction between
the atoms forming covalent bond.
• They are neither hard nor brittle, except quartz and diamond.
• They exhibit relatively low melting and boiling points except
quartz and diamond.
• They are poor electrical conductors, except polar molecules
conduct electricity in an aquesious solution.
 Theories of covalent bonding
• The most important theories of covalent
bonding are ;
The Lewis theory,
The valance bond theory and
The molecular orbital theory.
 1. The Lewis Theory (the Octet rule)
Lewis theory explains covalent bond formation based on
the octet rule (Atoms share electron pairs until they
have eight electrons on their valance shell)
• explain the formation of covalent bond based on the
achievement of inert gas configuration or the octet rule.
• Hydrogen will share e-’s until it feels 2 e-’s like Helium.
• Other elements share e-’s to achieve what is called a
“Stable Octet” (8 valence e-’s)
 Steps in writing Lewis formula
1.Write the electron configuration of all atoms in the molecule
2. Add the number of valence electrons of all atoms.
3. Decide the central atom to which the surrounding atoms are
directly bonded.
a. Atoms with a fewer number are usually the central atom while
those with larger number of atoms in a molecule are the
surrounding atoms.
b. Hydrogen, oxygen, and halogen atoms are usually the
surrounding atoms.
c. When two or more carbon atoms are in a molecules they are
bonded to each other to form a chain, and oxygen atoms are
bonded to each other in peroxide and super oxides.
d. In most acids like H2SO4, HNO3, H2CO3, hydrogen atoms are
bonded to oxygen atoms.
e. Atoms with larger atomic size are usually the central atoms
where as smaller and more electronegative elements are the
surrounding atoms.
g. Atoms which require larger number of electrons to complete
their octet are usually central atoms so that they are able to
share more electrons from many different surrounding atoms.
4. Place a pair of electrons between the central atom and the
surrounding atoms. You can use a single line to connect the
central atom to the surrounding atoms. Here subtract the number
of electrons used from the total number of valance electrons.
5. Complete the octet of the surrounding atoms except for H, Li, Be,
and Al.
6. Place any remaining electrons on the central atom as lone pairs.
7. If the octet of the central atom is still not complete, complete its
octet by using electron pair or pairs from the surrounding atom
forming multiple bonds (double or triple bond).
 Electron-dot formula for Ammonia (NH3)
(Lewis structure)
1. Electron Configuration 1H = 1S1
N = 1S2 2S2 2P3
7
2. The total No of valence electron in NH3,
1N = 1x5 = 5
3H = 3x1 = 3,
8 total Valence electrons of NH3 molecule
3. Nitrogen is the central atom

4. Place a pair of electrons between N-atom and each of the H-atom

 Conti…..Lewis structure

6. Here the octet of the central N-atom is incomplete. Thus place the
remaining pair of electrons on the central N-atom as a lone pair
 Exceptions to the Octet rule
• Incomplete Octet
Molecules with an atom having fewer than eight
valance electrons around it
e.g. BeF2 & BF3
• The Expanded Octet
Molecules with an atom having more than eight
valance electrons around it.
e.g. PCl5 & SF6
A. Incomplete Octet……..
 B. The Expanded Octet
The octet rule is also broken where atoms have an extra energy level
PF3 obeys the octet rule, but PF5 does not. PF5 has ten outer electrons
and uses one 3S, three 3P and one 3d orbital

C. The octet rule does not work in molecules which hav

e an odd number of electrons such as NO and ClO2.
 2. The valence Bond (VB) Theory
 A covalent bond is formed when the orbital of
two atoms overlap and are occupied by a pair of
electrons that have the highest probability of
being located between the nuclei.
Three central themes of VB theory
• Opposite spins of electron pairs
• Maximum overlap of bonding orbital
• Hybridization of atomic orbital;
(sp,sp2,sp3, sp3d, and sp3d2)
 Overlap of atomic orbital's
 In order for a covalent bond to form between two atoms,
overlap must occur between the orbitals containing the
valence electrons.
• The two orbital's share a common region in space

• The merging of overlapping orbitals occurs either end-to-

end or side-to-side
• sigma bond (σ);When two atomic orbitals overlap to build
up electron density along the axis joining the nuclei of
bonding atoms, (s-s, s-p, or p-p)
• Pi (π) bond; On the other hand, a bond formed by lateral
overlap of P- orbitals.
• It is formed by partial overlap of P-orbitals
Dotted areas: representation of "electron cloud" for one electron

"Head-on Overlap"

Sigma Bond: merged orbital, 2 e's

The σ-bonds in ethylene (The shared electron pair
occupies the region directly between the atoms
 Hybridization of atomic orbital
 Atomic orbital are mixed up together to give a new orbital that have
relatively higher bond forming power.

 In order for “best overlap” to occur, valence electrons need to be re-

oriented and electron clouds reshaped to allow optimum contact.

 To form as many bonds as possible from the available

valence electrons, sometimes separation of electron
pairs must also occur.

 We describe the transformation process as “orbital

hybridization” and we focus on the central atom in the species...
 “sp” Hybridization: all 2 Region Species

Be 2
BeCl 2 Cl Be Cl 2Cl 14
16 e's/2= 8 prs

Cl Be Cl (octet violator)

Number of regions around CENTRAL ATOM: 2

Cl Be Cl shape : LINEAR
bond angles: 180o
Hybridization of Be in BeCl2

Valence e’s
Hybrid sp orbitals:
1 part s, 1 part p
Atomic Be: 1s2 2s2

Energy

2p separate "hybridize"
2p

"sp" "sp"

2s 2s
 "arrange"
Be is said to be
Be
"sp hybridized"
(VSEPR)

FORMATION OF BeCl2:

Each Chlorine atom, 1s22s22p63s23p5 , has one

unshared electron in a p orbital. The half filled
p orbital overlaps head-on with a half full hybrid
sp orbital of the beryllium to form a sigma bond.
 Cl Be Cl

Cl Be Cl

Cl Be Cl

sp hybridized, linear, 180o bond angles

 “sp2” Hybridization: All 3 Region Species

F
B 3
BF 3 F B F 3F 21
24 e's/2= 12 prs

F B F (octet violator)

Number of regions around CENTRAL ATOM: 3

F shape : TRIGONAL PLANAR

bond angles: 120o
B
F F
 Hybridization of B in BF3

Hybrid sp2 orbitals:

Valence e’s 1 part s, 2 parts p

Atomic B : 1s2 2s2 2p1

Energy

2p separate "hybridize"
2p

"sp2" "sp2" "sp2"

2s 2s
 "arrange"
B is said to be
B
"sp2 hybridized"
(VSEPR)

FORMATION OF BF3:

Each fluorine atom, 1s22s22p5, has one unshared

electron in a p orbital. The half filled p orbital
overlaps head-on with a half full hybrid sp2 orbital
of the boron to form a sigma bond.
 sp2 hybridized, TRIGONAL PLANAR,
120o bond angles

F
F

B
B
F F
F F
“sp3” Hybridization: All 4 Region Species

C 4
CH 4 H 4H 4
8
H C H 8 e's /2 = 4 pr

Number of regions around CENTRAL ATOM: 4

H
shape : TETRAHEDRAL
bond angles: 109.5o
C
H H
H
 Hybridization of C in CH4

Valence e’s Hybrid sp3 orbitals:

1 part s, 3 parts p
Atomic C : 1s2 2s2 2p2

Energy

2p separate "hybridize"
2p

"sp3" "sp3" "sp3" "sp3"

2s 2s
 "arrange"
C is said to be
C "sp3 hybridized"
(VSEPR)

FORMATION OF CH4:

Each hydrogen atom, 1s1, has one unshared

electron in an s orbital. The half filled s orbital
overlaps head-on with a half full hybrid sp3 orbital
of the carbon to form a sigma bond.
 sp3hybridized, TETRAHEDRAL,
109.5o bond angles

H
H

C C

H
H H H

H H
 Unshared Pairs, Double or Triple Bonds

Unshared pairs occupy a hybridized orbital the same as

bonded pairs: See the example of NH3 that follows.

Double and triple bonds are formed from electrons left behind and unused
in p orbitals. Since all multiple bonds are formed on top of sigma bonds,
the hybridization of the single () bonds determine the hybridization and
shape of the molecule...
 Home Work 1

Describe Hybridization of C and shape of following

species:
CO, CO2, HCN, CH2O, CO32- , CBr4

C O O C O H C N

O O 2 Br

C C C
H H O O Br
Br
Br
“sp3d” Hybridization: All 5 Region Species

F
P 5
F F 5F 35
PF5 P
40
F 40 e's /2 = 20 pr
F
F
F F
P
F
F

Number of regions around CENTRAL ATOM: 5

F
F shape : TRIGONAL BIPYRAMIDAL
bond angles: 90, 120, 180o
P F
F
F
Hybridization of P in PF5 P: 1s2 2s2 2p6 3s2 3p3

Energy

3d 3d

separate

3p 3p

3s 3s

"hybridize"

3 3 3 3 3
"sp d" "sp d" "sp d" "sp d" "sp d"
 "arrange"
P is said to be
P "sp3d hybridized"
(VSEPR)

FORMATION OF PF5:

Each fluorine atom, 1s22s22p5, has one unshared electron in a p orbital. The half
filled p orbital overlaps head-on with a half full hybrid sp3d orbital of the phosphorus
to form a sigma bond.
 sp3d hybridized, TRIGONAL BIPYRAMIDAL,
90, 120, 180o bond angles

F F

F F

P F P F

F F

F F
“sp3d2” Hybridization: All 6 Region Species

F
S 6
F F 6F 42
SF6 S
48
F F
48 e's /2 = 24 pr
F
F
F F
S
F F
F

Number of regions around CENTRAL ATOM: 6

F
F F shape : OCTAHEDRAL
bond angles: 90, 180o
S
F F
F
 Hybridization of S in SF6 S: 1s2 2s2 2p6 3s2 3p4

Energy

3d 3d

separate

3p 3p

3s 3s

"hybridize"

3 2
"sp d "
 "arrange"
S is said to be
S "sp3d2 hybridized"
(VSEPR)

FORMATION OF SF6:

Each fluorine atom, 1s22s22p5, has one unshared electron in a p orbital. The half
filled p orbital overlaps head-on with a half full hybrid sp3d2 orbital of the phosphorus
to form a sigma bond.
 Home Work 2

Describe hybridization of S and shape of species

in SF2, SO2, SO32- , SF3+, SF4, SF5-

2-
S
S S
F
O O O O
F O

F F
F F
S S S
F F F F
F
F F F
Summary: Regions, Shapes and Hybridization

#, regions shape hybridization

2 linear sp
2
3 trigonal sp
planar
3
4 tetrahedral sp
3
5 trigonal sp d
bipyramidal
3 2
6 octahedral sp d
 summery
IF you can draw a Lewis structure for a species,
and count electronic regions around central atom,
you can immediately determine:

• the shape of the species about the central atom

• the hybridization of the species based on the

central atom
 3. Molecular Orbital Theory
 Molecular orbital theory focuses on another approach to covalent
bonding in molecules using molecular orbitals.
 A molecular orbital describes a region of space in a molecule
where electrons are most likely to be found.
 Molecular orbitals are formed by combining atomic orbitals on
different atoms.
 Molecular orbital theory is not able to certainly explain how
covalent molecules are formed but it is able to estimate
The energies of molecular orbitals
Shapes of molecular orbital
Strength of bond in a molecule,
Molecular stabilities and
Magnetic properties
 Bonding and antibonding MO’s
• Molecular orbitals are formed when atomic orbital are
combined together
• There are two types of molecular orbital; (depending on the
combination modes)
Bonding Molecular orbitals
 Is lower, in energy than the atomic orbitals
 The two wave function of the atomic orbitals have the same
signs (++ or – – signs), their combination will be added up,
Anti-bonding Molecular orbitals
 Is higher in energy than the atomic orbitals
 The wave functions of both atomic orbitals are difference (+ –
or – + signs), their combination is subtraction
 Linear combination of Atomic Orbital (LCAO)

The central themes of molecular orbited theory include the

formation of molecular orbital, their energy and shape
and how they fill with electrons these can be explained by
Linear combination of Atomic Orbital
Rules for linear combination of Atomic Orbital
1. The atomic orbitals must be roughly of the same energy.
2. The orbitals must overlap one another as much as
possible. This implies that the atoms must be closer
energy for effective overlap.
3. In order to produce bonding and anti bonding MOs, either
the symmetry of the two atomic orbitals must remain
unchanged when rotated about the inter-nuclear line, or
both atomic orbitals must change in an identical manner.
Combining Atomic Orbitals
Energy levels diagram of molecular orbital
 No. e- in bonding MOs - No. e- in antibonding MOs
Bond Order =
2
 Conti….
The stability of molecules can be determined from bond order
The higher the bond order,The stronger the bond is.
The lower the bond order, implies no net stability
Electrons fill MOs follows just as they fill atomic orbitals,

 No two electrons in the same molecule can have all four

quantum numbers the same (Pauling exclusive principle)

 Orbital are filled in order of increasing energy (the Aufbau

principle)

 Orbital of equal energy are half-filled with spins parallel ,before

any is filled (the Hund‘s rule )
The order of energy of molecular orbital has been
determined mainly from spectroscopic data

In the case of B2, C2, and N2 there is a slightly different ordering in

orbital energies. For example, B2 has 3 + 3 = 6 valence electrons.
Energy levels diagram of molecular orbital
For Z < 8
Energy levels diagram of molecular orbital
For Z > 7
 Molecular orbital treatment for different
molecules
• Homo-nuclear diatomic molecules
H2+
He2
B2
• Hetro-nuclear diatomic molecules
NO
CO
CN-
Energy levels diagram of H2+.
Energy levels diagram of He2 molecule
Energy levels diagram of B2 molecule.
 Molecular orbital treatment for hetro-nuclear
diatomic molecules

• The same principles apply for explaining the

formation hetronuclear diatomic molecules

• The two atoms are of different type

• The energy of the atomic orbitals is different.

• The electron of the higher electronegativity atom has
lower energy level
Energy levels diagram of NO molecule.
 Energy levels
diagram of CO
molecule.
Energy levels diagram of CN- molecule.
MOLECULAR
SHAPES
OF
COVALENT
COMPOUNDS
 Theories of molecular shape
• Atoms in individual covalent molecules are
arranged in a three dimensional spaces in to a
definite geometrical shapes.
What factors determine atoms to be arranged around the
central atom?

• Theories of molecular shape :

 The Sedgwick-Powell theory
 Valence shell electron pair repulsion theory(VSEPR)
 The Sedgwick-Powell theory
• Molecular shape is defined by the relative
positions (arrangement) of the atom around the
central atom
• molecules and ions that only contain single
bonds, the approximate shape can be predicted
from the number of electron pairs in the outer
or valence shell of the central atom.
• the electrons pairs are orientated in space as far
apart as possible.
 Important points of
Sedgwick-Powell theory
• two pairs of electrons…… linear geometry
• three electron pairs ……..triangular planar
• four electron pairs ……..,tetrahedral
• five electron pairs ……..trigonal bipyramidal
VSepR tHEORY
 What Vsepr means
 What kind of electrostatic repulsion force do you expect in
molecules which contain both bond pair and lone pair electrons
around the central atom?
 The core principle of the VSEPR theory is that, the
arrangement of atoms in a space around the central
atom and with respect to each other is determined by
the repulsion between the valence shell electrons and
the number of electrons around the central atom.
 Since electrons do not like each other, because of their
negative charges, they orient themselves as far apart
as possible, from each other
 This leads to molecules having specific shapes
 Things to remember
 Bonded electrons take up less space than un-bonded/unshared
pairs of electrons.
 There are three different types of electrostatic repulsion force
between electrons pair in molecules that contain both bond pair and
lone pair electrons around their central atom. These are:
1.bond pair and bond pair repulsion (bp – bp)
2. bond pair and lone pair repulsion (bp – Lp)
3. Lone pair and lone pair repulsion (Lp – Lp)
 Lp – Lp electron repulsion > Lp – bp electron repulsion > bp –
bp electron repulsion repulsion
 Triple bond has high replusion than double bond and single
bond.
 Linear
EXAMPLE:

BeF2
CO2, BeH2
•Number of Bonds = 2
•Number of Shared Pairs of Electrons = 2
•Bond Angle = 180°
 Trigonal Planar
EXAMPLE:

GaF3 , BF3, BCl3

•Number of Bonds = 3
•Number of Shared Pairs of Electrons = 3
•Number of Unshared Pairs of Electrons = 0
•Bond Angle = 120°
 Bent #1
EXAMPLE:

H2O
•Number of Bonds = 2
•Number of Shared Pairs of Electrons = 2
•Number of Unshared Pairs of Electrons = 2
•Bond Angle = < 120°
 Bent #2
EXAMPLE:

O3
•Number of Bonds = 3
•Number of Shared Pairs of Electrons = 3
•Number of Unshared Pairs of Electrons = 1
•Bond Angle = >120°
 Tetrahedral
EXAMPLE:

CCl4, SiCl4CH4

•Number of Bonds = 4
•Number of Shared Pairs of Electrons = 4
•Number of Unshared Pairs of Electrons = 0
•Bond Angle = 109.5°
 Trigonal Pyramidal
EXAMPLE:

NH3
•Number of Bonds = 3
•Number of Shared Pairs of Electrons = 3
•Number of Unshared Pairs of Electrons = 1
•Bond Angle = <107.5°
 Trigonal bI-Pyramidal
EXAMPLE:

PCl5 , NbF5

•Number of Bonds = 5
•Number of Shared Pairs of Electrons = 5
•Number of Unshared Pairs of Electrons = 0
•Bond Angle = <120°
 OCTAHEDRAL
EXAMPLE:

SF6
•Number of Bonds = 6
•Number of Shared Pairs of Electrons = 6
•Number of Unshared Pairs of Electrons = 0
•Bond Angle = 90°
Summary of molecules and their shapes
The molecular shape with two electron groups
• BeH2, CO2, H2O (linear, bent)
Molecular shape with three electron groups
• BF3, SO3, and BCl3 ( triagonal pyramidal )
Molecular shapes with four electrons groups
• CH4, SiCl4, ClO4 and CCl4 (tetrahedral
Molecular shapes with five electrons groups
• PC15 ( triagonal bi-pyramid)
Molecular shape with six electron groups
• IF5 , XeF4 , SF6 ( octahedral )
THE METALLIC
BONDING
 What is metallic bond?
• Metallic bonding refers to a chemical bond of the
type that holds of metallic solid.
• the valance electrons of the atoms are not bound
to any atom in the metal
• (the electrons) are delocalized over the entire
crystal , lifting the inner as positively charged
• metallic bonding is the mutual attraction between
the delocalized electron (called free electrons)
and the positive ion of the metallic solids.
 Theories of metallic bonds
• These theories (model) helps to explain how
metallic bond is formed

1 Electron sea models

2 Band theory
 The electron sea model
• The electron sea model of metallic bonding proposes that all the
metal atoms in the sample contribute their valence electros to
form an electron sea that is delocalized throughout the
substance.
• The metal ions (the nuclei with their core electrons) are
submerged with in this electron sea in an orderly way.
• The piece of metal is held is together by the mutual attraction of
the metal cations for the mobile, highly delocalized electrons.
• The existence of these free electrons (delocalized electrons)
accounts for the high electrical and the thermal conductivity of
metals, like silver, copper, gold and aluminum.
Conti….The electron sea model
 Band theory
• The lower energy MOs are occupied by the valence
electrons and make up the valence band.
• The empty MOs that are higher in energy make up
the conduction band.
• The valence and conduction bands are contiguous
• Electrons can jump from the filled valence band to
the unfilled conduction band by small quantity of
energy (the electrons are completely delocalized)
Band of molecular orbital's in Na metals.
 Differences b/n ionic, covalent and metallic bond

In contrast to ionic bonding,

The metal ions are not held in place as rigidly as
in an ionic sold.
In contrast to covalent bonding,
no particular pair of metal atoms is bounded
through any localized pair of electrons. Rather,
the valence electrons are shared among the entire
atom in the substance.
 General properties of metals
 They are solids with moderate to high melting points and
much higher boiling points.
 They typically bend or bent rather than crack or shatter.
 They can be flatted in to sheets (malleable) and pulled in to
wires (ductile).
 They are exceptionally good conductors of electricity and
thermal in both solid and liquid states,
 They readily form alloys solid mixtures of variable
composition, example bronze (70-95 % Cu, 1-25% Zn and 1-
18% Sn ) and Brasses (50-80 % Cu, 20-5 % Zn )
 Crystals (solid)
• In a solid, atoms, molecules, or ions occupy
specific positions called lattice points.
Types of Crystals (solids).
Crystalline solids
• : - genenerally have a well defined
shape, because their particles (atoms, molecules, or
ions) occur in a highly order arrangement. (celestite,
pyrite, amethyst, and halite )
• Amphorous solids : - have poorly defined shape
because they lack extensive molecular level ordering
of their particles. (e,g glass)
 Types of solid
• Solids are also often classified according to their chemical
bonding, structures and properties
 Molecular solids contain discrete molecular units held by
relatively weak intermolecular forces
 Metallic solids have atoms bound by delocalized electrons
that give metallic conduction.
 Covalent or polymeric solids have atoms bound by directional
covalent bonds, giving relatively low coordination numbers in
a continuous dimensional network.
 Ionic solids are bound by electrostatic attraction between
anions and cations (every anion is surrounded by cations and
vice versa)
 Structure of Ionic solids
• The structures of many ionic solids can be
accounted for by considering the relative sizes
of the positive and negative ions, and their
relative number

• It is possible to predict the type of ion

coordination from the ratio of the cation to
anion size by Radius ratio rules.
 Radius Ratio Rules
• An ionic solid should achieve maximum
electrostatic stability when
(i) Each ion is surrounded by as many as
possible ions of opposite charge, and
(ii) The anion-cation distance is as short as
possible.
Radius ratio = atomic radii cation / atomic radii of
anion
 Limiting radius ratios and structures
Limiting radius Coordination Shape
(ratio ( r+/ r- )) number
• < 0.155 2 Linear
• 0.155 - 0.225 3 planar triangle
• 0.225 - 0.414 4 Tetrahedral
• 0.414 - 0.732 5 Square planar
• 0.414 - 0732 6 Octahedral
• 0.732 - 0.99 8 Body centered cubic
 The crystal lattice and the unit cell
• crystal lattice; the lattice consists of all points
within identical surroundings.
• unit cell ;The smallest portion of the crystal
that is repeated in all three directions
 Types of crystal system (Close packing )
The packing of spheres to occupy the minimum amount of
space ( the arrangement of close neighbor atoms)

Hexagonal close packing

Three layers of atoms.

 The top and bottom layers contain

six atoms

 Three atoms nestled between the

atoms of the top and bottom layers
 Conti… Types of crystal system

Cubic close packing (Cubic system)

 8 atoms at the corner of
cube
 Types of cubic unit cell

Simple cubic unit cell

Body-centered
Face-centered
 The simple cubic unit cell

The centers of eight particles defined the corners

of cube
Each particles touch along the cube’s edges, but
they do not touch diagonally along the cubic’s
faces or through its center
 The body – centered cubic unit cell:
eight particles lie at each corner and one in the
center of the cube.
Those at the corners do not touch each other,
but they all touch the one in the center.
 The face –centered cubic unit cell
eight particles lie at each corner and four in the
center of each face but not in the center of the
cubic. Those at the corners touch those in the
faces but not each other. The coordination
number is 12.
Summary of simple cubic unit cell
 Packing efficiency
• is the percentage of the total volume occupied
by the spheres themselves.
• The packing efficiency measures how the
particles are packed in a give volume.
• For a particles of the same size, the higher the
coordination number of the crystal is, the
greater the number of particles in a given
volume.
 packing efficiency of different unit cells
simple cubic unit cell : 52% of the available unit cell
volume is occupied by spheres and 48% consists of
empty space between them. (very inefficient way to
pack sphere ).
body – centered cubic cell : has a packing efficiency of
68% (much higher than the simple cubic unit cell)
face – centered cubic unit cell : has a packing efficient
of 74% and the coordination number is 12.
 Classification of ionic structures

• depending on the relative number of positive

and negative ions, ionic compounds can be
grouped into ; AX1, AX2, AX3, (where A is
cation and X is anion )
 Type AX
 Three structural arrangements commonly found
zinc sulphide,
 The coordination 4. (4:4 arrangement)
 The arrangement is a close-packed arrangement
Sodium chloride
 An octahedral arrangement
 The coordination is 6 ( 6:6 arrangment )
 Considered as a cubic close-packed arrangement.
 Type AX2
• The three most common structures are fluorite
(CaF2), rutile (TiO2) and SiO2
Structure of fluorite ;
• each Ca2+ ion is surrounded by eight F- ions
• The coordination numbers are 8 and 4
• four Ca2+ ions are tetrahedral arranged around each
F- ion
• adopts a face-centered cubic arrangement
 Conti……type AX2
Structure of rutile ( TiO2 )
• each Ti4+ is octahedral surrounded by six O2- ions
• each O2- ion has three Ti4+ ions round it in a plane
triangular arrangement.
• the coordination numbers are 6 and 3 (6:3
arrangement )
• is a distorted body-centered cubic lattice.