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Crystal Structure
Packing Spheres
Close-packed Structure
Crystal Defect
X-Ray Diffraction by Crystals
Miller Index
Types of Crystals
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CRYSTAL STRUCTURE
The periodic arrangement of atoms in the crystal

SOLID
CRYSTALLINE AMORPHOUS

•Having a regular and continuous •Having a random or disordered

three-dimensional arrangement of arrangement in the solid state, that
atoms in the solid state is antithesis or opposite of crystalline
•Possesses rigid and long-range order •solid formed rapidly : glass
•Its atom, molecules or ions occupy •lack a regular three-dimensional
specific positions arrangement of atoms
•Accurate melting point •Inaccurate melting point
•Crystallization : process of forming
crystals from a liquid or gas
•What forces responsible for the
stability of a crystal?
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UNIT CELL

The smallest component of the crystal, which when stacked together

with pure translation repetition reproduce the whole crystal

Basic repeating structural unit of a crystalline solid

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LATTICE POINT
 An infinite arrays of points in space in which each points has
identical surrounding to all others

A unit cell

Its extension in three dimensions.

The spheres or points
BLUE
are not necessarily individual atoms,
but are included to show the necessary symmetry – lattice point
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monoclinic

triclinic orthorhombic

crystal
systems
cubic tetragonal

trigonal hexagonal
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7 CRYSTAL SYSTEMS – BRAVAIS LATTICE
Crystal Relations between Examples Lattice Number
systems edges & angles of symbol of lattice
unit cell
triclinic abc CuSO4.5H2O P 1
      90° K2Cr2O7
monoclinic abc Na2CO3 P, C 2
 =  = 90°   120°
orthorhombic a  b  c AgNO3 P, I, F, C 4
 =  =  = 90°
tetragonal a=bc KH2PO4 P, I 2
 =  =  = 90°
hexagonal a=bc SiO2 P 1
 =  = 90°  = 120°
trigonal a=b=c CaCO3 R 1
 =  =   90°
cubic a=b=c NaCl P, I, F 3
 =  =  = 90°
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CUBIC SYSTEM
LATTICE SYMBOL : PRIMITIVE UNIT CELL(P)
z



b
y

a

x a, b, c = lattice constant (vectors)

 ,  ,  = angles form by these vectors
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CUBIC
SYSTEM

SIMPLE CUBIC BODY-CENTRED FACE-CENTRED

(SCC) CUBIC (BCC) CUBIC (FCC)

Unit cell : Unit cell : Unit cell :

primitive (P) body-centred (I) face-centred (F)
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PACKING SPHERES
The way the spheres are arranged in layers determines
what type of unit cell we have
Arrangement of identical spheres in a simple cubic cell

Top view of one layer

of spheres Definition of a simple
cubic cell
Since each sphere is
shared by eight unit cells
and there are eight
corners in a cube, there is
the equivalent of one
complete sphere inside a
simple cubic unit cell
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COORDINATION NUMBER (CN)
The number of atoms (or ions) surrounding an atom (or ion)
in a crystal lattice

The larger the coordination number,

the closer the spheres are to each other

Cubic system Coordination number

Simple cube (SCC)

6
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Cubic system Coordination number

Body-centred cube
(BCC)

8
Face-centred cube
(FCC)

12
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FACE CENTRED CUBIC (FCC)

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COUNTING ATOM IN UNIT Atoms in different positions in a cell are

CELL shared by differing numbers of unit cells
CORNER/VERTEX: atom shared by 8 cells 1/8 atom per cell

An atom on a corner/vertex is shared by eight

unit cells

EDGE : atom shared by 4 cells 1/4 atom per cell

An atom on an edge is shared by four unit cells

FACE : atom shared by 2 cells 1/2 atom per cell

An atom on a face is shared by two unit cells, so

only half of the atom belongs to each of these cells.

BODY : unique to 1 cell 1 atom per cell

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Cubic system Number of atom

Simple cube (SCC)

8 corners x 1/8 = 1 atom

Body-centred cube (BCC)

(8 corners x 1/8) + 1 body = 2 atoms

Face-centred cube (FCC)

(8 corners x 1/8) + (6 faces x 1/2) = 4 atoms

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ATOMIC RADIUS
Distance between the centre atom to the
centre of neighbour atom in the crystal
The atomic radius can be calculated :
• atoms in the crystal are sphere
• the spheres are touching with their neighbours
• type of structures and lattice constants are known

Cubic system Radius, r

Body-centred cube (BCC) a3
(lattice constant = a) 4
Simple cube (SCC) a
(lattice constant = a) 2
Face-centred cube (FCC) a2
(lattice constant = a) 4
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The relationship between the edge length (a) and radius (r)
of atoms in the simple cubic cell, body-centred cubic cell
and face-centred cubic cell

a = 2r
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b = 4r b2 = a2 + a2
b2 = a2 + a 2 c2 = a2 + b2
4r = a2 + a2 = 3a2
4r = 2a c = 3 a = 4r
a = 4r a = 4r
2 3
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Question 1:
For face-centred cube with lattice constant a. Show the calculation to prove
that the atomic radius is a2
4

r a2 + a2 = (4r)2
r
a2 + a2 = 4r
r a
r 2a2 = 4r

a 2a = 4r

r = 2a
4
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CRYSTAL DENSITY
n = no of atom in one cell unit
 = n x M M = molecular weight of crystal
a3 N N = Avogadro no. (6.023 x 1023)
 = density
a = edge length
Gold (Au) crystallize in a cubic close-packed structure (the face-centred cube, FCC)
and has a density of 19.3 g/cm3. Calculate the atomic radius of gold

Step 1:get the volume

 = n x M
a3 N

19.3 g/cm3= 4 x 197.0

a3 6.023 x 1023
a3 = 6.78 x 10 –23 cm3

a3 = 6.79 x 10-23 cm3 x 1 x 10-2 m 3

x 1 pm 3

1 cm 1 x 10-12 m
a3 = 6.79 x 107 pm3
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Step 1:get the mass of a unit cell and volume

m = 4 atoms x 197.0 g Au x 1 mol

1 unit cell 1mol Au 6.023 x 1023 atoms

m = 1.31 x 10-21 g / unit cell

V = m = 1.31 x 10-21 g / unit cell = 6.79 x 10-23 cm3

 19.3 g/cm3

V = 6.79 x 10-23 cm3 x 1 x 10-2 m 3

x 1 pm 3

1 cm 1 x 10-12 m
V = 6.79 x 107 pm3

V = a3
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Step 2:get the edge length (a) of the cell

V = a3
a =3
6.79 x 107 pm3
= 408 pm

Step 3: radius of an Au sphere (r) is related to the

edge length by

a = 4r
2
r = 408 2
4
= 144 pm
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CLOSE-PACKED STRUCTURE
The most efficient arrangement of spheres – there is a least waste of space

a single layer of spheres is

X closest-packed with a HEXAGONAL
coordination of each sphere

• a second layer of spheres is placed in

the indentations left by the first layer
X
•space is trapped between the layers that is
not filled by the spheres
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When the third layer of spheres is placed

in the indentations of the second layer
there are TWO choices :

• The third layer lies in indentations

directly in line (eclipsed) with the 1st
layer

-Layer ordering may be described as ABA

-Example : Mg, Ti, Zn, He, Co, Be, Cd

The third layer lies in the alternative

indentations leaving it staggered with
respect to both previous layers

-Layer ordering may be described as ABC

-Example : Al, Ni, Au, Cu, Ca, Pb, Pt, Ag
and all solid noble gases except helium
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Structures are not close-packed
Body-centred cube (bcc) structure : there is a sphere at a centre of a
cube with spheres at each corner

Examples: Ba, Mn, Fe, Cr, W and alkali metals (Na, K)

Less closely packed than the ccp and hcp structures ( for which the
coordination number is 12)
Primitive cubic structure (scc) in which spheres are located at the
corners of a cube

More empty space in the simple cubic and body-centred cubic cells than
in the face-centred cubic cell.
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CRYSTAL DEFECT

•Regular pattern of atomic arrangement is interrupted

by crystal defects

•A “perfect” crystal of NaCl - would consist of alternating

Na+ and Cl− ions on an infinite three-dimensional and a

simple defect (a vacancy) would be a missing Na+ or
Cl− ion.

•Various types of defects are:

-POINT DEFECTS
-LINE DEFECTS
-PLANAR DEFECTS
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The properties of pure metals can be modified by adding atoms of

other elements to their crystalline structure. A mixture of elements
that retains the properties of metals is called an alloy.
Two types of alloys are;
Substitutional alloys have some of
the host metal atoms replaced by other
metal atoms of similar size.
E.g. Brass, sterling silver, pewter
Interstitial alloys have some of the
small holes in the structure occupied
by small atoms.
E.g. Steel
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POINT DEFECTS
Point defects : where an atom is
missing or irregular place
in the lattice structure.

an extra atom that has crowded its

way into an interstitial void in the
crystal structure

an atom of a different type than the

bulk atoms, which has replaced one of
the bulk atoms in the lattice.
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much smaller than the atoms in the bulk

matrix. Interstitial impurity atoms fit into
the open space between the bulk atoms
of the lattice structure.

empty spaces where an atom

should be, but is missing.
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LINE DEFECTS - dislocations

•Dislocations are linear defects around which some of the atoms

of the crystal lattice are misaligned.

•There are two basic types of dislocations :

-EDGE dislocation
-SCREW dislocation

1) Edge dislocations are caused by the termination of a plane

of atoms in the middle of a crystal.
2) Adjacent planes are not straight, but instead bend around
the edge of the terminating plane so that the crystal structure
is perfectly ordered on either side.

3) Screw dislocation is a result of shear stress, but the defect

line movement is perpendicular to direction of the stress and
the atom displacement, rather than parallel.
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PLANAR DEFECTS

•Grain boundaries occur where the crystallographic direction

of the lattice abruptly changes. This usually occurs when two
crystals begin growing separately and then meet.

•Anti phase boundaries occur in ordered alloys: in this case,

the crystallographic direction remains the same, each side of
the boundary has an opposite phase: For example if the
ordering is usually ABABABAB, an anti phase boundary takes
the form of ABABBABA.

•Stacking faults occur in a number of crystal structures, but

the common example is in close-packed structures. Face-
centered cubic (fcc) structures differ from hexagonal close
packed (hcp) structures only in stacking order
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X-RAY DIFFRACTOMETER
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X-RAY DIFFRACTOMETER
A beam of X-rays is directed at a mounted crystal : single crystal
Atoms in the crystal absorb some of the incoming radiation and reemit it :
the process is called scattering of X-rays
The shield prevents the strong undiffracted X-rays from damaging the
photographic plate
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C
Fe
H2C
Cl

C
Fe
H2C
Cl

ORTEP diagram for chloroacetylferrocene. Showing the atom-labelling

schemes and 50% probability displacement ellipsoids for non-H atoms

• the ORTEP diagram depicts the bond distances and angles of the
molecule in the solid
• the atoms are displayed as ellipsoids that indicate the direction and
amplitude of their thermal motion
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X-RAY DIFFRACTION

X-ray diffraction the scattering of X-rays (electromagnetic radiation)

by the units of a crystalline solid

• lattice should be able to diffract X-ray because the wavelength of X-rays

(1Å = 10-10 m) is comparable in magnitude to the distances between lattice
points in a crystal

• X-ray diffraction technique offers the most accurate method for

determining bond lengths and bond angles in molecules in the solid state.
Why?
X-rays are scattered by electrons
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X-RAY DIFFRACTION

•X-ray energy can be related with wavelength distance with Planck formula:

E = h c = light halaju (3 x 108 ms-1)

= hc  = light frequency
  = wavelength distance (1Å = 10-10 m)
h = Planck constant (6.62 x 10-34 J)

Energy from X-ray : E = 6.62 x 10-34 J x 3 x 108 ms-1

10-10 m
= 19.86 x 10-16 Js-1
1eV = 1.6 x 10-19 J
 E = 19.86 x 10-16
1.6 x 10-19
= 12.4 x 103 eV
= 1.24 X 104 eV
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incident rays reflected rays

Bragg’s Law
 A 
2d sin = n
B   D d
C
d sin d sin
  2d because sin  1

• Consider the scattering of X-rays by atoms in two parallel planes

• Two incident rays are in phase with each other (their maxima and minima occur
at the same positions)
•The upper wave is scattered or reflected by an atom in the first layer while the
lower wave is scattered by an atom in the second layer
• In order for these two scattered waves to be in phase again, the extra distance
traveled by the lower wave must be an integral multiple of the wavelength () of
the X-ray; that is,
BC + CD = 2d sin  = n n = 1,2,3……
: is the angle between the X-rays and the plane of the crystal
d: distance between adjacent planes
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incident rays
reflected rays

 A 
d
B   D

d sin C d sin
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Question 2: BRAGG’S LAW

Distance between the planes {100 } of NaCl crystal is 3.0 Å. The rays are
reflected to this crystal to produce Bragg reflection in first order with the
incident angle 9°. Calculate the X-ray wavelength that has been used and
at what angle the second order reflection occur?

2d sin = n
First order, n = 1 Second order, n = 2
 = 2d sin sin = n
n 2d
= 2 x 3.0 x sin 9° = 2 x 0.94
 = 0.94 Å 2 x 3.0
  = 18.3°
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MILLER INDICES (hkl)

 Miller Indices (hkl) : A set of numbers which quantify the

intercepts and thus may be used to uniquely identify the
plane or surface

 Cubic crystal system (unit cell with dimensions a x a x a)

y
a
x a
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RULES FOR FINDING PLANES

Identify the intercepts on the x-, y- and z- axes

Specify the intercepts in fractional coordinates. Take the
reciprocals of the fractional intercepts
Express as integers
Divide the integers with the highest common factor
Enclosed in brackets (…) :
( ) for an individual plane
{ } for all planes of that crystallographic type
Replace negative integer with bar over the number –h to h
If the plane parallel to an axis, say it cuts at 
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Miller Indices : (1 0 0) x y Z

Intercept length a  
z

Reciprocal 1/a 1/ 1/

As integer 1 0 0
(cleared
y fractional)

Common factor 1 0 0
x

Miller indice (100)

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Other examples:
1. The (1 1 0) surface
x y Z

z
Intercept a a 
length

reciprocal 1/a 1/a 1/

As integer 1 1 0
(cleared
(0,a,0) fractional)
y Common 1 1 0
factor
x (a,0,0)
Miller indice (110)
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2. The (1 1 1) surface x y Z

z Intercept a a a
length

Reciprocal 1/a 1/a 1/a

(0,0,a)

As integer 1 1 1
(cleared
fractional)
(0,a,0)
y Common 1 1 1
factor
x (a,0,0)
Miller indice (111)
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3. The (2 1 0) surface
x y Z

z Intercept 1/2a a 
length

reciprocal 1 1 1
1/2a a 

As integer 2 1 0
(cleared
(0,a,0) fractional)
y
Common 2 1 0
factor
x (1/2a,0,0)
Miller indice (210)
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x y Z
z
Intercept 3/4a 1/2a 1/4a
length

Reciprocal

As integer
(cleared
y fractional)
Common
factor
x
Miller indice
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x y Z
z
Intercept 3/4a 1/2a 1/4a
length

Reciprocal 1 1 1
3/4a 1/2a 1/4a
As integer
(cleared 4 6 12
y fractional)
Common
factor 2 3 6
x
Miller indice (2 3 6)
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z x y Z

Intercept
length

Reciprocal

As integer
y
(cleared
fractional)
x
Common
factor

Miller indice (2 1 2)
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z x y Z

Intercept 1/2a a -1/2a

length

Reciprocal 1 1 -1
1/2a a 1/2a

As integer 2 1 -2
y
(cleared
fractional)
x
Common 2 1 -2
factor

Miller indice (2 1 2)
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z z
(1 0 1) (0 1 1)

y y

x x
z z

(0 0 1) (0 1 0)

y y

x x
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MILLER INDICES OF DIRECTION IN CUBIC

CRYSTALS
Direction of crystallographic (vector) is defined as a line which
joined any two point in the crystal lattice
In cubic crystals, all directions are perpendicular to planes with
the same indices
E.g. the direction [110] is perpendicular to the (110) plane

RULES FOR FINDING DIRECTIONS

Always start from origin
Put directions in [ ] or in < > for family of directions
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z

c
 
A B
D C
a

b
y
O G
x E F

Direction / vector OE = [100]

OD = [101]
OC = [111]
H
AE ? [101]
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direction [101] is perpendicular to the (101) plane

z

y
O

x
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TYPES OF CRYSTALS AND GENERAL PROPERTIES

TYPES OF FORCES HOLDING GENERAL EXAMPLES
CRYSTAL THE UNITS PROPERTIES
TOGETHER
IONIC Electrostatic Hard, brittle, high NaCl, LiF, MgO,
attraction melting point, poor CaCO3
conductor of heat and
electricity
COVALENT Covalent bond Hard, high melting point, C(diamond),
poor conductor of heat SiO2(quartz)
and electricity

MOLECULAR Dispersion forces, Soft, low melting point, Ar, CO2, I2, H2O,
dipole-dipole forces, poor conductor of heat C12H22O11(sucrose)
hydrogen bonds and electricity

METALLIC Metallic bond Soft to hard, low to high All metallic

melting point, good elements: Na, Mg,
conductor of heat and Fe, Cu
electricity
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IONIC CRYSTAL

 Ionic bond – two ions are bound together

 The lattice points are occupied by ions
 Ionic lattice – positive and negative
ions attract to each other to form
3D continuous lattice structure
 Properties of ionic lattices :
a) Melting point & boiling point high
b) Electrical conductivity – do not conduct
c) Hardness - hard
d) Brittleness – brittle CaF2

 Binary compounds
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Crystal Structure Examples

Rock-salt NaCl, LiCl, LiF, LiBr, LiI, KBr, RbI,
AgCl, AgBr, MgO, CaO, TiO, FeO,
NiO, SnAs, CoO, CdO, VO, MnO,
SrO, BaO,
Cesium chloride CsCl, CsBr, CsI, TlCl, TlBr, TlI,
CsSH, CaS, TlSb, CsSn, CuZn
Sphalerite - Zinc blende ZnS, CuCl, CdS, HgS,

Wurtzite ZnS, ZnO, BeO, MnS

Fluorite CaF2, BaCl2, HgF2, PbO2

Antifluorite K2O, K2S, LiO2, Na2O, Na2Se,

Na2S
Rutile TiO2, MnO2, SnO2, WO2, MgF2,
NiF2
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Types of crystal structure:
 Rock-salt – Sodium chloride (NaCl)- halite

Cl- Na+

Cl-

Na+
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Coordination Number (CN) : (6,6)

Cl- Na+ Number of ions in a unit cell

8Cl- (corners) x 1/8 = 1 Cl- ion

6Cl- (faces) x 1/2 = 3 Cl- ions
Total = 4 Cl- ions

12Na+ (edges) x 1/4 = 3 Na+ ions

1Na+ (body) x 1 = 1 Na+ ion
Total = 4 Na+ ions

Ratio of cation and anion – 4:4  1:1

Chemical formula = NaCl

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 Cesium chloride (CsCl)

Cl-

Cl- Cs+
Cs+
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Coordination Number (CN) : (8,8)

Cl- Cs+

Number of ions in a unit cell

8Cl- (corners) x 1/8 = 1 Cl- ion

1Cs+ (body) x 1 = 1 Cs+ ion

Ratio of cation and anion – 1:1

Chemical formula = CsCl

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 Sphalerite – Zinc blende (ZnS)

S2- Zn2+
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Coordination Number (CN) : (4,4)

S2- Zn2+
Number of ions in a unit cell

8S2- (corners) x 1/8 = 1 S2- ion

6S2- (faces) x 1/2 = 3 S2- ions
Total = 4 S2- ions

4Zn2+ (body) x 1 = 4 Zn2+ ions

Ratio of cation and anion – 4:4  1:1

Chemical formula = ZnS

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 Wurtzite – ZnS
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Number of ions in a unit cell

S2- Zn2+
4S2- (edges) x 1/4 = 1 S2- ion
2S2- (faces) x 1/2 = 1 S2- ion
7S2- (body) x 1 = 7 S2- ions
Total = 9 S2- ions

8Zn2+ (corners) x 1/8 = 1 Zn2+ ion

4Zn2+ (faces) x 1/2 = 2 Zn2+ ions
4Zn2+ (edges) x 1/4 = 1 Zn 2+ ion
5Zn2+ (body) x 1 = 5 Zn 2+ ions
Total = 9 Zn2+ ions

Ratio of cation and anion – 9:9  1:1

Chemical formula = ZnS

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 Fluorite – CaF2

F- Ca2+
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Coordination Number (CN) : (8,4)

F- Ca2+ Number of ions in a unit cell

8F- (body) x 8 = 8 F- ions

8Ca2+ (corners) x 1/8 = 1 Ca2+ ions

6Ca2+ (faces) x 1/2 = 3 Ca2+ ions
Total = 4 Ca2+ ions

Ratio of cation and anion – 4:8  1:2

Chemical formula = CaF2

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 Rutile – TiO2

O2- Tiiv
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Coordination Number (CN) : (6,3)

O2- Tiiv Number of ions in a unit cell

4O2- (faces) x 1/2 = 2 O2- ions

2O2- (body) x 1 = 2 O2- ion
Total = 4 O2- ions

8Ti4+ (corners) x 1/8 = 1 Ti4+ ions

1Ti4+ (body) x 1 = 1 Ti4+ ion
Total = 2 Ti4+ ions

Ratio of cation and anion – 2:4  1:2

Chemical formula = TiO2

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Preferred Lattice
Hole Structure for Coordination
Number of Examples
r hole / r Range number of
Geometry Larger Ion cation:anion
(cation,anion)

hexagonal Wurtzite
closest- (ZnS)
Tetrahedral packed 4:4
0.225-0.414 (4,4)
  cubic Zinc Blende
closest- (ZnS)
packed
hexagonal Rutile (TiO ) 2

closest- (6,3) 2:4

 Octahedral packed
0.521-0.732
cubic Sodium
closest- (6,6) 4:4 Chloride
packed
Cesium
cubic
(8,8) 1:1 Chloride
Cubic
0.732<r<1.00 cubic
  Fluorite
closest- (8,4) 4:8 (CaF )
packed 2
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RADIUS RATIO

Compound A+B- was formed by A+ atom with atomic

radius r+ and B- atom with atomic radius r-

P = radius ratio
P = r + / r- r+ = radius of cation
r- = radius of anion

Example : radius ratio of Na+ / Cl-

= 0.95 Å / 1.81 Å
= 0.53 Å
0.53 Å in range 0.521-0.732 so the structure is
octahedral with coordination number (6,6)
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COVALENT CRYSTAL Examples : diamond, graphite, quartz(SiO2)

Atoms are held together by covalent bonds
Two allotropes of carbon : diamond & graphite
DIAMOND : 1) each atom carbon – sp3-hybridized (bonded with 4 atom carbon)
2) bond angle & bond distance?
3) strong covalent bonds – hardest material
4) high melting point = 3550°C

Structure of diamond
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142pm

Carbon atoms are arranged in six-membered ring

sp2-hybridized (each atom is covalently bonded to three other atoms)
Each layer of graphite –delocalized molecular orbital : electrons are free to
move around – good conductor of electricity in directions along the planes of
carbon atoms
The layers – held together by weak Van der Waals forces – the layers can
slide over one another, slippery to the touch and is effective as a lubricant, in
pencils, in ribbon for computer printers and typewriters
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MOLECULAR CRYSTAL

Examples : H2O, CO2, O2, O3, CH4, P4

The lattice points are occupied by molecules

Attractive forces between them are Van der Waals and or hydrogen
bonding
Intermolecular hydrogen bonding responsible for maintaining the 3D
lattice of ice
Molecular crystal-more easily broken apart than ionic and covalent
crystals – Van der Waals and hydrogen bonding quite weak
Most crystals melt at temperature below 100°C
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METALLIC CRYSTAL
• Metallic bonds are bonds that occur between metallic elements

• Metallic bond is the electrostatic attraction between positive ions

and delocalised electron. Valence electron form electron
clouds/electron sea.

• The electrons are free to move in between the atoms and around
them, and they hold all the atoms together in the process

• An interesting fact about metallic bonds:

1. the weakest of all the bond types. They form fairly soft metals.
2. electrons can move so freely around the atoms. These metals are
excellent conductors of electricity : COPPER, GOLD
- - - - - - - - -
+ + + +
- - - - - - - - -
The strength of metallic bond is
proportionate to the number of
+ + + +
- - - - - - - - -
valence electron in the element
+ + + +
- - - - - - - - -
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LATTICE ENERGY
►Lattice energy (LE) of an ionic compound is the change in internal
energy that accompanies the formation of one mole of the solid from
its constituent gas-phase ions at 0 K.
Example : K+ (g) + Cl- (g) KCl (s) H = -701 kJ/mol
►Lattice energy is to measure the electrostatic attractions and the
repulsions of the ions in the crystal lattice
►To determine the theoretical value, using the Born-Landé equation :

U = -NA z + z - ē2 1 – 1
n
4°r°
N = Avogadro’s number (6.023 x 1023 mol-1)
A = Madelung constant (1.748) n = the average Born exponent
z+ = the relative cation charge, z - = the relative anion charge
ē = the actual electron charge (1.602 x 10 -19 C)
 = 3.142 ° = 8.854 X 10-12C2.J-1.m-1
r° = the sum of the ionic radii (internuclear distance between ion centre)
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►Example :
Estimate the lattice energy of NaCl using an electrostatic model following the data:
Madelung constant (A) = 1.748
Ionic radii for Na = 116pm, Cl = 167pm
Born exponent = 8

U = -NA z + z - ē2 1–1
4°r° n

= -(6.023 x 1023 mol-1)(1.748)(1)(1)(1.602 X 10-19 C)2 1–1

8
4 x 3.142 x (8.854 x 10-12 C2.J-1.m-1)(2.83 x 10-10)
= -751 kJ/mol

►From the Born-Landé equation, the value of LE depends on the:

Ion charge (z) : z LE
Ionic radii (r) : r LE
Internuclear distance between ions (r°) : r° LE
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►Example :

compound MgCl2 MgO

z+ x z - (2x1)=2 (2x2)=4
LE (kJ/mol) -2493 -3889

Ion Na+ K+ F- Cl- Br-

r (nm) 0.095 0.133 0.136 0.181 0.195

compound NaF NaCl KBr

r°(nm) 0.231 0.277 0.328
LE(kJ/mol) -3880 -771 -670

Exercise :
Estimate the lattice energy of NaF using an electrostatic model. A = 1.74; Born
exponent NaF = 7; internuclear Na-F distance = 231pm

Answer : -901 kJ/mol

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BORN-HABER CYCLE
Thermochemical cycle called the Born-Haber
Born-Haber Cycle : process of considering the series of component
reactions that can be imagined as the individual steps in compound
formation
Example :
Calculate the lattice energy for NaCl formation
H1
Na(s) + ½ Cl2(g) NaCl(s)
H2 H4 H1 = -413kJ/mol (standard enthalpy of NaCl formation)
H6
H2 = 109kJ/mol (atomization enthalpy of Na) =
Na(g) Cl(g) sublimation energy
H3 H5 H3 = 495kJ/mol (ionization energy of Na)
H4 = 123kJ/mol (atomization enthalpy of Cl)
Na+(g) + Cl-(g)
H5 = -369kJ/mol
246 kJ/mol (bond dissociation
(electron affinity of energy
Cl) for Cl 2)

Solution : H1 = H2 + H3 + H4 + H5 + H6

Lattice energy (H6) = H1 - (H2 + H3 + H4 + H5)
= -771 kJ/mol
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Consider the reaction between lithium and fluorine:

Li(s) + ½ F2(g) LiF(s)

The standard enthalpy change for this reaction is -594.1 kJ/mol

(standard enthalpy of formation for LiF).
SUM of enthalpy changes for the steps is equal to the enthalpy change for
the overall reaction (-594.1 [Link])

Convert solid Li to vapor Li (sublimation) :

Li(s) Li(g) Hsubl = +155.2 kJ/mol

Dissociate ½ mole of F2 gas into separate gaseous F atoms:

½ F2(g) F(g) Hdiss = +75.3 kJ/mol
Ionize 1 mole of gaseous Li atoms:
Li(g) Li+(g) + ē HIE = +520kJ/mol
First ionization of lithium
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Add 1 mole of electrons to 1 mole of gaseous F atoms (electron affinity):

F(g) + ē F-(g) HEA = -328 kJ/mol
Combine 1 mole of gaseous Li+ and 1 mole of F- to form 1 mole of solid LiF:
Li+(g) + F-(g) LiF(s) H = ?

H1
-594.1
Li(s) + ½ F2(g) LiF(s)

H2 +155.2 H4 +75.3

Li(g) + F(g)
H? H6
H3 +520 H5 -328
Li+(g) + F-(g)

Solution :
H1 = H2 + H3 + H4 + H5 + H6
Lattice energy (H6) = H1 - (H2 + H3 + H4 + H5)
= -1017 kJ/mol
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EXERCISES :
1) Draw the Born-Haber Cycle and calculate the energy change (in
kJ/mol) for the formation of the following substances from their
elements:
CaF2
Sublimation energy for Ca = +178.2 kJ/mol
Bond dissociation energy of F2 = +158 kJ/mol
First ionization energy of Ca = +589.8 kJ/mol
Second ionization energy of Ca = +1145 kJ/mol
Electron affinity of F = -328 kJ/mol
Lattice energy of CaF2 = -2630 kJ/mol (ANSWER : -1215 kJ/mol)

2) Calculate the energy change for the formation of solid LiBr from the
elements with the following data : sublimation energy for Li is +159.4
kJ/mol, bond dissociation energy for Br2 is +224 kJ/mol, the energy
necessary to convert Br2 (liquid) to Br2 (gas) is 30.9 kJ/mol, lattice
energy for LiBr is -807 kJ/mol, ionization energy for Li is +520 kJ/mol and
electron affinity for Br is -325 kJ/mol
(ANSWER : -309.7 kJ/mol)
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3) Calculate a lattice energy for CaH2 (in kJ/mol) using the following
informations:
Eea for H = -72.8 kJ/mol
I1 for Ca = +589.8 kJ/mol
I2 for Ca = +1145 kJ/mol
Heat sublimation for Ca = +178.2 kJ/mol
Bond dissociation energy for H2 = +435.9 kJ/mol
Net energy change for the = -186.2 kJ/mol
(ANSWER : -2389.5 kJ/mol)
formation of CaH2 from its elements