Solid state Chemistry CHM 4101

• Credit: 3 (3+0)
• Contact hours: 3hrs per week
Monday 8-10 am
Wednesday 8-9 am
• Semester: 1st semester 2008/2009
• Prerequisite: CHM 3101 and CHM 3301
• Lecturers: Dr. Tan Kar Ban
• Prof. Zobir Hussein
60 marks (assignment, quiz, test 1,2 and 3)
40 marks (final exam)

References: Solid state chemistry and its applications, A.R. West

Basic solid state chemistry, A.R. West
Solid state Chemistry, Hannay, N.B
 SOLID STATE CHEMISTRY
The preparation and characterisation of solids-involves wide range of
preparation methods, e.g.

i. Conventional solid state method- shake ‘nbake methods, grinding

and then fired in furnace, not atomic scale mixing.
ii. Chimie douce (soft chemistry)- under moderate conditions, usually
low temperature,Topotactic (structural elements of the reactants are
preserved in the product, but the composition changes.
iii. Ball milling- grinding media rotate around the grinding medium which
filled with raw materials

iv. Other methods, e.g. sol gel, hydrothermal synthesis, intercalation

and deintercalation,vapour phase transport

(synthesis methods, West,chapter 9)

.
• Why study solids? SOLIDS ARE OF IMMENSE
TECHNOLOGICAL IMPORTANCE- superconductor, Solid oxide
fuel cell (SOFC), lithium ion battery, electronic and electrical
components, automobile parts, nuclear waste disposal etc.

• The study of solids leads to the preparation of new solids with

improved/new technological properties- oxides are flexible in
structure, the properties are possibly to be tailor-made

• The study of advanced functional materials such as

electroceramics and structural ceramics
-involves many disciplines including chemistry, physics,
mechanical engineering, materials science and metallurgy.

- applications of electroceramics involve electrical and

magnetic properties whereas applications of structural
ceramics mainly rely on their mechanical behaviour (Segal,
1991).
Examples of electroceramics (Segal, 1991)

Materials Application
YBa2Cu3O7-x,BiSrCaCu2Ox,Ti2BaCuO6 High Tc superconductor
Al2O3, AIN, BeO Substrates, packaging
BaTiO3, SrTiO3 Capacitors
ZnO-Bi2O3 Varistors
Pb(Zr, T)O3 (PZT) Piezoelectrics
SnO2, ZrO2 Gas sensor
(MnZn)Fe2O4, BaFe12O19 Magnets
LiNbO3, Pb(La, Zr, Ti)O3 (PLZT) Electro-optics
Fluoride glasses Infrared optics
ZnS, CdS Phosphors
INORGANIC SOLIDS AND MOLECULES
Inorganic solids are different from molecules

MOLECULES INORGANIC SOLIDS

eg benzene eg NaCl, sodium chloride

Single units Infinite lattices

Fixed formulae Variable stoichiometry

Defects not allowed Defects unavoidable

Properties vary with

Properties are fixed
composition
 Structures, Properties, and
Applications of Solids
• When substances freeze, or separate
as a solid from solution, they tend to
form crystals
• Crystals have highly regular features
and are said to possess symmetry or be
symmetrical
 SOLIDS

Most of the things we encounter every day are solids: clothes, furniture,
buildings, cars, etc

Definition of solids

A crystalline solid is a solid in which the atoms, ions or molecules lie in

an orderly array (NaCl)

An amorphous solid is a solid in which the atoms, ions or molecules lie

in random positions (glass, rubber)
• Not all solids are crystalline
• Glass is a general term used to refer to a
noncrystalline or amorphous solid
• Amorphous solids lack the long-range
repetitive internal structure found in
crystals
• For this reason they are sometimes called
supercooled liquids, a term suggesting
the kind structural disorder found in liquids
• Crystalline structure can be determined
using the technique of X-ray diffraction
• Crystals can be divided into four types:
ionic, molecular, covalent, and metallic
– Ionic crystals have cations and anions at
the lattice sites
• Tend to be brittle, have high melting points, and
are nonconducting in the solid phase and
conducting in the liquid phase.
– Molecular crystals have neutral molecules
at the lattice sites
• Due to the relatively weak intermolecular
attractions, solids made from small molecules
tend to be soft with low melting points. They are
nonconducting in both the liquid and solid
phase.
– Covalent crystals have atoms at the lattice
sites covalently bonded to other atoms
• These are also called network solids and the
crystal is essentially one large molecule. A
typical example is diamond which is very hard,
has a very high melting point, and is a
nonconductor of electricity.
Each carbon atom in
diamond is covalently
bonded to four others at
the corners of a
tetrahedron. The structure
extends throughout the
entire crystal.
– Metallic crystals have cations at the lattice
sites surrounded by mobile electrons
• Metallic crystals conduct heat and electricity
well, have metallic luster, and tend to have high
melting points.
A highly simplified view of
a metallic solid. Metal atoms
lose valence electrons to the
solids as a whole and exist
as positive ions surrounded
by a mobile “sea” of
electrons.
 TYPES OF SOLIDS

Solids are classified according to the type of interactions between the

particles forming the crystal
There are: METALLIC, IONIC, covalent and molecular solids

METALLIC SOLIDS
Metals (Ti, Ca)
Metallic bond

IONIC CRYSTALS
Oxides, halides etc (CaO, NaCl)
Ionic bond + cation

- anion
 STRUCTURE OF SOLIDS
The structure of crystals influences their physical properties strongly

Structure of a crystalline solid: how atoms, ions molecules are

arranged with respect to one another

Atoms or ions in solids are conveniently represented by spheres

A crystalline solids is viewed as built from atoms or ions, which repeat with
regularity
Lattice : an infinite array of points in space (lattice points), in which each
point has identical surroundings to all of the other lattice points

lattice
• The symmetry, or repetitive pattern, in
crystalline solids is called a lattice
• The particles that make up the lattice
are called lattice points
• The basic repeating unit in a lattice is
called the unit cell
• Starting from a unit cell, the entire lattice
can be generated by repeating the unit
cell in all directions
• The same unit cell can describe many
different structures
 Basic Crystallography
The description of the ordering of atoms in a solid comes from simple
concepts of how identical objects stack in an array
Assuming the atoms are round and packed
as close as possible

Some Basic Definitions

• LATTICE = The smallest component of
the crystal, which when stacked together with pure translational repetition
reproduces the whole crystal.

• CRYSTAL STRUCTURE = The periodic arrangement of atoms in the

crystal.

• COORDINATION NUMBER= The atoms which are coordinated to a

particular atom within the unit cell, i.e. nearest neighbouring atoms
UNIT CELL- the simplest
repeating unit which represents
the whole crystal structure-
three uniques
crystallographic
axies , a,b, c

-described by associating with

each lattice point a group of
atoms called the MOTIF
(BASIS)
-The angles of the edges of the
unit cell need not be 90 or 120
degrees
-The figure shows a possible
crystal structure and its unit cell
.
Number of Atoms in 3D Cells (unit formula, Z)
Atoms in different positions in a cell are shared by differing numbers of unit
cells
Contribution of different
positional atoms

Vertex atom shared by 8

cells = 1/8 atom per cell

Edge atom shared by 4 cells

= 1/4 atom per cell

Face atom shared by 2 cells

= 1/2 atom per cell

Body unique to 1 cell, 1

atom per cell
Bravais lattices
Combining 7 Crystal Classes with 4 possible unit cell types Symmetry
indicates that only 14 possible BRAVAIS LATTICES
 Shapes of Unit Cells
All the possible shapes of a unit cell are defined by 7 crystal systems,
which are based on the relationship among a,b,c and , , ,

a  b  c ;       90 Cubic system

a  b  c ;       90 Tetragonal system

a  b  c ;       90 Orthorhombic system

a  b  c ;       90 Rhombohedral (trigonal) system

a  b  c ;     90;   120 Hexagonal system

a  b  c ;     90   Monoclinic system

a  b  c ;       90 Triclinic system

 TEST

a = b  c;  =  =  = 90
a = b = c;  =  =  = 90 c
a
a Cubic a Tetragonal
a
a

a  b  c;  =  =  = 90 a  b  c;  =  = 90,   90

c
c
Orthorhombic  b Monoclinic
b a
a

c
a  b  c;       90

a = b = c;  =  =   90  
a a
b Triclinic
a a Rhombohedral
 a c

a 
a b
a
Sim ple Face-centered Body-centered Sim ple End face-centered
CUBIC M O NOCLINIC Types of unit cells


+
c

a
a Shapes of unit cell
a
b
a
Sim ple End face-centered Body-centered Face-centered Sim ple
ORTHORHO M BIC RHOM BOHEDRAL

14 Bravais lattices
c c
c 
a  
o a b
a 120 a
a
Sim ple Body-centered
HEXAGONAL TRICLINIC
TETRAG ONAL
Bravais lattices define unit cells. When combined with translational
operations they give raise to 230 space groups, i.e there are 230 possible
space-filling patterns that atoms, ions or molecules can adopt in the 3D
space
Summary
There are seven crystal systems defined by unit cell parameters
a,b,c and , β,  and four bravais lattice types:
primitive (P), Body centered (I), face centred (F) and side centred (A, B, C,)

Combining these 14 Bravais lattices with all possible symmetry elements

230 different Space Groups- F d 3 m, C2/c

Cubic a=b=c =β= =90° (P,F,I)

Orthogonal
Tetragonal a=bc =β= =90° (P, I)
Orthorhombic abc =β= =90 ° (P, F, I, A, B or C)

Hexagonal / trigonal
Monoclinic
Non-Orthogonal
Triclinic
• The simplest and most symmetrical three-
dimensional lattice is called a simple cubic
or primitive cubic lattice

(a) A simple cubic unit cell showing the lattice points.

(b) A portion of a simple cubic lattice. (c) Only a
portion of each atom of a substance that forms a simple
cubic lattice lies within a particular unit cell.
• Only 1/8 of each atom lies in a particular
simple cubic unit cell
• Each simple cubic unit cell contains:
1/8 atom
8 corners   1 atom
corner
• Two additional cubic lattices are
possible: face-centered cubic (fcc) and
body-centered cubic (bcc)
Lattice points in a fcc unit cell
are found at each of the eight
corners and in the center of each
face. A fcc unit cell contains 1
atom from the eight corners plus
6*1/2=3 atoms from each face
for a total of 4 atoms.

Lattice points in a bcc unit cell

are located at each of the eight
corners and in the center of the
unit cell. A bcc unit cell contains
2 atoms.
 Types of Unit Cells

Primitive lattice: the unit cell has a lattice point at each

corner only (P)

Body centred lattice: the unit cell has a lattice point at

each corner and one in the centre (I)
Face-centred lattice: the unit cell has a lattice point at
each corner and one in the centres of one pair of
opposite faces (A), (B), (C)

All-face-centred lattice: the unit cell has a lattice point

at each corner and one in the centre of each face (F)
 Unit Cell Parameter and Volume of a CCP (FCC) Unit Cell

CCP = FCC Face Centre Cubic a  b  c ;       90

In the FCC cell the atoms touch along the face diagonals

r is the radius of the atom

a is the parameter of a cubic unit cell
2r
a
1 3
a  82 r V  a3  8 2 r 3 a

Maths help: the Pythagoras theorem c

a
For any right-angled triangle
a b c
2 2 2

b
 Density of a CCP (FCC) Unit Cell

mass
d
volume

mass of the unit cell = sum of the masses of the atoms in the unit cell
(n)

mass of one atom = molar mass divided by the Avogadro constant

NA

nM
N nM
d A 
3 3
8 2 r 3 8 2 r 3N
A
Important! there are four atoms in one CCP (FCC) unit cell
 WORKED PROBLEM
Question: Al has a CCP arrangement of atoms. rAl= 1.423 Å =143 pm.
Calculate the lattice parameter of the unit cell and the density of Al (atomic
weight = 26.98) in g/cm3

Answer: CCP has a FCC unit cell. Cell contents: 4 atoms/cell [8 at corners
(1/8 each), 6 in faces (1/2 each)
1 1
a  8 2 r  8 2  1.423  4.025 Å
Al

d 4M
3
82 r 3 Al N
A
4  26.98g  mol 1
d  2.698g  cm 3
3
8 2  (1.423  10 8 cm )3 (6.022  1023 mol 1)
Can be simplified as
D= Mass/ volume= FW/ molar volume
= FW/ (volume of formula unit x N)
N= Avogadro’s number,
If the unit cell, of volume V, contains Z formula units,
V= volume of one formula unit x Z
Therefore,
D= FW x Z / (V x N)
V= expressed in term of Å3 and must be multiplied by 10-24
to give densities in unit g/cm3

D= FW x Z x 1.66 / V
 Fractional Coordinates

Coordinates, which identify the position of an atom or ion in a unit cell

Fractional coordinates (x, y, z) are expressed as fractions of the length of the

sides of the unit cell (a, b, c)

c
b
(0.5, 0.5, 0.5)
a
(0, 0, 0) (0, 0, 0)

(0, 0, 0)

(0.5, 0, 0.5) (0, 0.5, 0.5)

(0.5, 0, 0.5)

(0, 0, 0) (0.5, 0.5, 0)

• A number of metals and compounds
have cubic lattices

Copper and gold both crystallize in a fcc structure. The

unit cell in gold is larger because copper atoms are
smaller than gold atoms.
Chloride ions in NaCl are associated with the lattice points of
a fcc unit cell. The sodium ions are placed between the
chloride ions.
• The stoichiometry of the unit cell must
match the stoichiometry of the
compound
Both ZnS and
CaF2 have fcc
unit cells.
Particles must
be weighted
correctly to
recover the
stoichiometry
of the
compound.
A unit cell of NaCl shows how to weight lattice points:
corners have a weight of 1/8, faces a weight of 1/2, and
edges a weight of 1/4. This unit cell contains four sodium
and four chloride ions.
• The packing of particles is also important
• Structures that achieve the maximum packing
density are called closest-packed
structures
• Different ions usually have different sizes
• Using spheres of the same size helps
visualize the different way layers can pack
• In closest-packed structures:
 Arrangement of atoms (Spheres)
Close packed spheres of the same size in 3D is a little complicated- leads to
possibility of two unique structures, depending on how planes of 2D
closest packed spheres are layered. i.e. HCP (hexagonal closed packing) or
CCP (cubic closed packing)

Hexagonal Closed Packing

-ABABAB layers
arrangement
Coordiantion
number: 12
74.04% unit cell
volume filled
Cubic Closed Packing
The ABCABC layers arrangement adopted Face Centered Cubic (fcc)
structure.
-12 nearest neighbors and the atoms fill 74.04% of unit cell
volume
If the edge lengths to be different and the right angles are maintained,
orthorhombic cell can be created
Different interstitial sites within FCC structure

Octahedral site (Oh)- 6-coordinated environment

Tetrahedral (Td)- 4-coordinated environment
How many Oh and Td sites within the FCC structure?
 Non Closed packing
Apart from closed packing layers arrangement, the body cubic
cell (bcc) structure adopted neither HCP nor CCP structures.
- the atoms occupying only 68.02% of the available unit cell
volume
- Coordination number: 8
Examples of Binary Structures derived HCP and CCP
layers arrangement
 Sodium chloride (NaCl)

CCP Cl- with Na+ in all Octahedral holes

Lattice: fcc
Motif: Cl at (0,0,0); Na at (1/2,0,0)
4NaCl in unit cell
Coordination: 6:6 (octahedral)
Cation and anion sites are topologically identical
 Nickel Arsenide (NiAs)

HCP As with Ni in all Octahedral holes

Lattice: Hexagonal - Primitive
a = b, c ~ 8/3a
Motif: 2Ni at (0,0,0) & (0,0,1/2) 2As at (2/3,1/3,1/4) & (1/3,2/3,3/4)
2NiAs in unit cell
Coordination: Ni 6 (octahedral) : As 6 (trigonal prismatic)
 Lattice Planes, Miller Indices and D-spacings
• Imaginary planes on or between which atoms lie – used as a reference grid to
which atoms in the crystal structure may be referred
• Guide to understanding X-ray interaction with matter and are specific to
symmetries and crystal systems
• The interplanar spacings are called d-spacings (Å)
• Lattice planes are assigned indices – Miller Indices, hkl (reciprocal of
intercept along a,b and c respectively)

c Planes intercept axes at:

½ a, parallel to b and c
b hkl = 200
a

If the crystal system is known, the d-spacing of a particular set of hkl

planes can be calculated from unit cell parameters and vice versa
A concept used to describe Braggs Law of Diffraction
Determination of Crystal Structure by X-ray diffraction

2dsin = n
Generation of X-rays n
How X-rays interact with Matter 2dsin
 Generation of X-rays
Energy released as X-rays
Cu
Electromagnetic radiation atom
sample 3s
Spectrum of X-rays

Cu e- W
beam 2p

Be
sample From characteristic target KLM lines,
I k1 need to “fine tune” the 

kβ k2 For structural studies, need monochromatic

radiation.
Filter white radiation and kβ (Ni)

Emission spectrum of Cu  (Å) Use Ge crystal monochromator to obtain k1 only

Cu k1 radiation,  = 1.541 Å heads towards the sample….

How does X-ray Interaction with Matter produce the XRD
profile?

There are two main factors that determine powder diffraction patterns:

(i) Size and shape of unit cell

(ii) Atomic number and position of atoms in unit cell

Identify

Characterise
 (i) Interaction with Lattice planes in a Crystalline Material – Bragg concept
Significance of peak positions
Two X-ray beams (1,2) are diffracted from adjacent planes in the crystal (A,B).
Under what conditions are 1’ and 2’ in phase?
For this, the extra distance travelled by 22’, xyz, must be a whole number of s (n).
D-spacing and angle of incidence, , are related to distance xy , therefore xyz :

Incident Diffracted
1 radiation 1’ radiation
Xyz = 2dsin
A 2   2’
Xyz = n 
2dsin = n  z d-spacing
B x
y
If Bragg’s law is satisfied, beams are in phase and interfere constructively – peaks!
At other angles, beams are out of phase and cancellation occurs.

X-ray interaction with lattice planes gives peak positions.

From this, if allowed symmetry (space group) is known, can calculate
hkl values, d-spacings and unit cell parameters
(ii) Interaction with the Atoms on and between Lattice Planes
Significance of peak intensities

Some important facts:

X-rays are diffracted/scattered by the electrons surrounding the

nucleus of an atom

Amount of scattering determines the peak intensities

So, heavy atoms are strong X-ray scatterers (high z value, many
electrons)

Ihkl depends on the nature of atoms on and between the lattice planes
The X-ray beam (electromagnetic wave) sets each electron of an atom
vibrating. These emit radiation which is in phase or coherent with
the incident beam. Act as a secondary point source of X-rays so:

X-rays scattered by an atom are the resultant of the secondary X-rays

scattered by each electron in the atom, in the form of a wave
If all electrons scatter in phase with the incident X-ray beam then
the total scattered intensity is the sum of the individual
intensities, known as:

Scattering factor or form factor (f)

proportional to atomic number, z, i.e., to the number of
electrons which the atom possess

Depending on where different atoms are in the unit cell, the

amount of in phase scattering from electrons surrounding these
atoms results in varying degrees of constructive or destructive
interference from the diffracted X-rays.

This causes variations in peak intensities at particular d-

spacings
 Summary

Size, shape and symmetry of unit cell

Peak positions (° 2, d-spacing) in a diffraction pattern
Enables us to Identify a compound

Atomic number and position of atoms in a unit cell

Peak intensities in a diffraction pattern
Enables us to Characterise and understand the structure
 Chemical Bonding
• Attractive forces that hold atoms together in compounds
are called chemical bonds.
• The electrons involved in bonding are usually those in
the outermost (valence) shell.
Types of Chemical Bonding
1. Metal with nonmetal:
electron transfer and ionic bonding

2. Nonmetal with nonmetal:

electron sharing and covalent bonding
3. Metal with metal:
electron pooling and metallic bonding
o Ionic bonding results from electrostatic
attractions among ions, which are
formed by the transfer of one or more
electrons from one atom to another.
o Covalent bonding results from sharing
one or more electron pairs between two
atoms.
The three models of chemical bonding
 Ion and ionic radii (West, pp69)
-Discussion of crystal structures requires information on the
size of ions in crystal
Crystal chemistry – ionic radii of Pauling , Goldschmidt and
Shannon and Prewitt.
Cations are larger and anions are smaller than previous
thought.
e.g. Pauling- Na+ =0.98 Å; F- = 1.36 Å
Shannon and Prewitt, 1.14 and 1.30 Å, respectively.-
sizes depend on coordination number
- Size can be estimated fairly accurate via high quality X-
ray diffraction and electron density map throughout
crystal.
• There are several trends in ionic radii that is familiar

– The radius increases as you move down a column.

Al+3 = 0.675 Å, Ga+3 = 0.760 Å, In+3 = 0.940 Å, Tl+3 = 1.025 Å

– The radius decreases as you move across a period.

La+3 = 1.172 Å, Nd+3 = 1.123 Å, Gd+3 = 1.078 Å, Lu+3 = 1.001 Å

The 4d & 5d metals have similar radii due to the lanthanide contraction.
Nb+5 = 0.78 Å, Ta+5 = 0.78 Å, Pd+4 = 0.755 Å, Pt+4 = 0.765 Å

– The cation radius decreases as you increase the oxidation state.

Mn+2 = 0.810 Å, Mn+3 = 0.785 Å, Mn+4 = 0.670 Å

– The radius increases as the coordination number increases.

Sr+2: CN=6 → 1.32 Å, CN=8 → 1.40 Å,
CN=10 → 1.50 Å CN=12 → 1.58 Å
Conclusion drawn:
1. Ions are essentially spherical
2. Ions maybe regarded as composed of two parts
a central core – most of the electron density is concentrated
an outer sphere- contains little electron density ( contradict
with oft-stated assumption that ions is charged,
incompressible, non-polarizable spheres.
3. Assignment of radii to ions is difficult; even for ions which are
supposedly in contact.
NB: ions are not hard sphere with clearly defined radius,
electron density does not decrease abruptly to zero at a
distance away from nucleus but decrease roughly
exponential with increasing radius.
Ions are elastic, flexible due to outer sphere.
see figure 2.3 pp 71. Ionic radii as a function of CN for cations.
Ionic structures – general principles
a. Ions are charged, elastic and polarizable
b. Ionic structures are held together by electrostatic forces
c. Maximum net attraction between ions (lattice energy)-
CN are as high as possible, provided the central ion
remain in close contact with its neighbouring opposite
charged ions- CN depends on size of ion
d. Repulsive force of anion-anion and cation-cation – far
apart as possible to achieve structure of high symmetry
with maximised volume.
e. Local electroneutrality prevails- valence of an ion = sum
of the the electrostatic bond strength between it and
adjacent opposite charged ions.
- Crystal treated as 3D array of point charges,
- Net Coulombic energy of the array
- F= (Z+e)(Z-e)/ r2
Z+e; Z-e= ions of charged
r = distance r
applied to each pair of ions in the crystal and evaluation of the
resulting force between ions leads to lattice energy.

- Maximising the volume- accustomed to min volume as

described from close-packing.
- Anion-cation attractive force limited by arise of repulsive force
when ions become too close which superposed by like ions.
- Constraints, e.g. cation-anion distances are minimised , higher
CN – like ions arrange themselves as far apart as possible- lead
to regular and high symmetrical arrays of ions which tend to
have maximised volumes. For example, Rutile structure.
Pauling’s electrostatic valence rule- charged on a
particular ion, e.g. an anion must be balanced by an
equal and opposite charge on the surrounding
cations
cations are shared around other anions , therefore,
requires estimation of effectively associated with
each cation-anion bond.
Electrostatic bond strength (ebs)
Ebs= m/n
For a cation Mm+ surrounded by n anions, Xx-
Σ m/n = x
Charge on anion must be balanced by the sum of the
ebs of the surrounding cations
• Example:
• Spinel, MgAl2O4
• Al3+ octahedral coordinated; Mg2+ tetrahedral
coordinated; O is surrounded tetrahedrally by three
Al3+ ions and one Mg2+.
• For Mg2+; ebs = 2/4 = ½
• For Al3+; ebs= 3/6 = ½
therefore, Σ ebs (3Al3+ + 1Mg2+) = 2
 The radius ratio rule
CNs of ions determined by consideration of electrostatic
force.- Max CN to maximize the lattice energy
Calculation of the octahedral cation site,(cation-cation and
anion anion are in contact
(2rx)2 + (2rx)2 = [ 2(rM+rx)]2
2rx√2 = 2(rM+rx)
rM/rx= √2 -1= 0.414
NB: if radius ratio< 0.414, cation is too small for octahedral
site and should occupy a site of smaller CN,
 0.414, the cation would push the anions apart up to
radius ratio of 0.732
Calculation of eight coordination site. e.g. CsCI
Cations and anions are in contact along the body diagonal of the cube
2(rM+ rx) = cube body diagonal
Anions are in contact along the cell edge
A = 2rM

Therefore,
2(rM+ rx) = 2rx√3
rM/rx = √3 -1 = 0.732
Calculation of tetrahedral site, e.g CaF2
Anion and cation are in contact along the body diagonals. Anions are
incontact along the cube face diagonals.
Use the tetrahedron as a cube with alternate coners missing
2rx = face diagonal
(2rx)2 + (√2rx)2 = [2(rM+rx)]2
i.e. 2(rM+rx)= √6rx

rM/rx (=√6 –2)/2 = 0.225

The minimum radius for various CNs can be summarised as

0.732< rM/rx < 1.00; CN= 8
0.414 < rM/rX , 0.732; CN= 6
0225< rM/rx < 0.414 ; CN= 4

If the cation radius decrease as anion radius remain constant, lead

to unfavorable overlap of anions in order to maintain optimal
cation-cation optimal contact
NB: Coordination number/ coordination environment
is determined by the radius ratio rule.
The cation-anion distance is determined by the
summing ionic radii
Corrdination Minimum radius
ratios

Linear, 2 -
Trigonal, 3 0.155
Tetrahedral, 4 0.225
Octahedral, 6 0.414
Cubic, 8 0.732
Dodecahedral, 1.000
12
-From the above table, one expects CN= 5
is absent as it is not possible to have a CN
of five in which all M-X bonds are of the
same length.
- Predicting trends in CN and structure type
qualitatively- depend strongly on the table
of ionic radii consulted. e.g. Rb/ I, radius
ration = 0.69 and 0.80 depending on the
tables. Size, rO2- = 1.40 Å and 1.26 Å,
respectively. (either, 8 or 6 coordinated?)
 Partial Covalent Bonding
• Covalent bonding- partial or complete occurs if
the outer electron charge density on an anion is
polarised towards and by a neighbouring cation
i. purely ionic structure- electron pair which
would be associated entirely with the anion is
displaced between the anion and cation
ii. Partial covalent bonding- some electron
density is common to both atoms but the rest is
associated with the more electronegative atom
• Examples:
• SrO, Bao and HgO.
SrO and BaO have rock salt structure and M2+ is
octahedrally coordinated. If based on size consideration
and if it was ionic, HgO should have the same structure.
in reality, only linear O-Hg-O segments derived from the
sp hybridization.

(Xe core)4f12 5d106s2

First excited state correponds to mercury (II)
(Xe core)4f12 5d106s16P1

Electron pair covalent overlap with an orbital on oxygen

AlF3, AlCI3 and AlBr3 – smooth transition from
ionic to covalent
AlF3- high melting point, ionic solid with a
distorted octahedral coordination of Al3+
(ReO3)
AlCl3- layered, polymeric structure in the
solid state similar to that of CrCI3 related to
the CdI2 and CdCI2
AlBr3 and AlI3- form dimeric unit formula of
Al2X6 (structure denoted in chapter 1, West)
In general, fluoride has high electronegativity, the form compounds mostly
ionic, covalent character increased as down the group 17, CI-Br-I.
 ENERGETICS OF IONIC BONDING
A compound adopts the structure that corresponds to the lowest Gibb’s energy
(G)

  
G  H  TS
The formation of a solid ionic compound from the gas of ions is so exothermic
that, at room temperature, the contribution of the change in entropy (S) to
the Gibb’s energy may be neglected

All the considerations on energetic of ionic solids will therefore focus on

changes in enthalpy (H)

is the Lattice Enthalpy (energy) and can be seen as the force that
H L holds ions together in a solid
 Evaluation of lattice energy
There are two ways of evaluating the Lattice Enthalpy (no direct measurements)
1 2

Experimentally Theoretically
Born-Haber cycle Born-Mayer equation
Kapustinskii equation

is the standard molar enthalpy change accompanying the formation

H L of a gas of ions from an ionic solid

MX ( s )  M  ( g )  X  ( g )
The disruption of a lattice requires energy and it is, therefore, an
endothermic process
This means that Lattice Enthalpies are always positive and the most stable
crystal structure of a compound is the structure with the greatest lattice
enthalpy under prevailing conditions
EXPERIMENTAL EVALUATION OF THE LATTICE ENERGY
Born - Haber Cycle: a closed path of steps (reactions), which include the
lattice formation of the compound MX from its constituent ions

Hess’s Law The enthalpy of a given chemical reaction is constant,

regardless of the reaction happening in one step or many
steps.

We need to define all the quantities included in a Born-Haber cycle

The standard enthalpy of decomposition of a compound into its elements in

their reference states is the negative of its standard enthalpy of formation

M ( s )  X(s)  MX(s) f H
MX ( s )  M(s)  X(s) - f H
Likewise the standard enthalpy of lattice formation from the gaseous ions
is the negative of the lattice enthalpy

MX ( s )  M  ( g )  X - ( g ) H L
M  ( g )  X - ( g )  MX(s) - H L

For a solid element, the standard enthalpy of atomisation  atom H
is the standard enthalpy of sublimation

M ( s )  M(g)  sub H 

For a gaseous element, the standard enthalpy of atomisation

is the standard enthalpy of dissociation

X 2 ( g )  2X(g)  dis H 
The standard enthalpy for the formation of ions from their neutral atoms is the
enthalpy of ionisation (for the formation of cations) and the electron-gain enthalpy
(for the formation of anions)

M ( g )  M  (g)  e - (g)  ion H 

X ( g )  e - (g)  X  (g)  eg H 

The value of the lattice enthalpy can be calculated from the requirement that
the sum of the enthalpy changes round a complete cycle is zero
• The energy change when NaCl forms can be
calculated using the ionization energy (IE) of
sodium, the electron affinity (EA) of chlorine,
and the lattice energy of NaCl

The energy needed to produce separated gaseous ions from

one mole of the solid is the lattice energy.
• Starting from 1 mole of gas phase atoms:
Na(g)  Na+(g) + e- +495.4 kJ (IE of sodium)
Cl(g) + e-  Cl-(g) -348.8 kJ (EA of chlorine)
Na+(g)+Cl-(g)NaCl(s) -787.0 kJ (-lattice energy)
Net: -640.4 kJ
• It turns out that for any ionic compound,
the chief stabilizing influence is the lattice
energy
• The size of the lattice energy depends on
ion size and charge
 – The lattice energy increases with charge
because the ions attract each other more
strongly
• Example: KCl (709 kJ) vs CaO (3401 kJ)
– Smaller ions have larger lattice energies
because they get closer together
• Example: NaCl (778 kJ) vs KCl (709 kJ) and
LiF (1033 kJ) vs LiCl (845 kJ)
• The lattice energy can be calculated
using a Born-Haber cycle
A Born-Haber
cycle for NaCl.
The upper and
lower paths must
give the same
energy change
because enthalpy
is a state
function: both
paths lead from
the elements to
solid NaCl.
 H /(kJ mol -1 )
Sublimation of + 89
K(s)

Ionisation of K(g) + 425

Dissociation of + 244
Cl2(g)

Electron gain by - 355

Cl(g)

Formation of - 438
KCl(s)
The lattice energy is equal to -x

  f H   sub H   ion H   eg H  H  0
* * * * *
L


H  (438  89  425  122  355) kJ mol  719 kJ mol
L
-1 -1

Only one chlorine atom from Cl2(g) is used to produce KCl and therefore
half of the dissociation energy of Cl2 is used
THEORETICAL EVALUATION OF
THE LATTICE ENERGY
• Ionic crystal treated as regular 3D arrays of point
charges.
• Two forces, 1. a)electrostatic repulsion and attractions in
the crystal and b) short range repulsive force
• The lattice energy, U= the net potential enegy of the
arrangement of charges that the structure, i.e. equivalent
to the energy required to sublime the crystal and convert
it into collection of gaseous ions.
• NaCI (s) → Na+ (g) +CI-(g), ΔH =U
• U depend son the crystal structure, charge on the ions
and internuclear seperation between the anion and
cation.
a) Electrostatic repulsive and attractive forces,
z z e 2
F
r2
Their coulombic potential energy, V, is given
2 by
r z z e
V   Fdr  
 r
b) Short range repulsive force- when two atoms or ions are
so close that their electron clouds begin to overlap. Bohr
suggested that this repulsive energy as
B
V n
r
B= constant and n is in the range of 5-12. n is large so that
V falls rapidly to zero with increasing r
 The lattice energy = net electrostatic
attraction/ repulsion and the Born repulsion
energy and finding the internuclear
separation, re, which gives the maximum U
value
Consider the rock salt structure, NaCI
- Cl
-
- +
+ - + + - +
- + -
- + -
r3 r6 + - + Na
- + -
r + - +
- r2 + -
r5 - -
+
+ - + + - +
- + -
 for NaCl
6Cl- at a distance r 6 Z  Z  e2
E coul  
12 Na+ at r√2 1 r
2
12e Z  Z 
8 Cl- at r√3 E coul  
2 2r
6 Na+ ar 2r 8e Z  Z 
2
E coul  
3 3r

Ecoul  E coul  E coul  E coul  ..........

1 2 3

6 Z  Z  e2 12 8 6
V  (6     .........)
r 2 3 4

Ecoul  
e2 (6 
12

8 6
  .....)
4 0 r 2 3 2

12 8 6
A  (6     .....)
2 3 2
A = Madelung constant
• The summation is repeated for each ion in
the crystal, i.e. 2N ions per mole of NaCI,
divided by 2 as each ion pair interaction is
counted twice.
z  z  e 2 NA
V 
r
• A= Madelung Constant which depends on
the geometrical arrangement of point
charges
See figure 2.5, lattice energy of ionic crystal as
a function of internuclear separation
If only the Coulombic attraction/repulsion – the
structure will collapse, V directly proportional
to -1/R.
z  z  e 2 NA BN
U   n
r r
dU e 2 Z  Z  NA nBN
therefore ,  2
 n 1
dr r r
du
when, O
dr
e 2 Z  Z  Ar n 1
B
n
e 2 Z  Z _ NA 1
hence, U   (1  )
re n
lattice energy of ionic crystal as a function of internuclear separation
Born-Mayer Equation: it shows the dependency of the lattice enthalpy from
the structure

NA z  z _ e 2    -1
U 1   ( J mol )
re  re 

N A is the Avogadro' s number

z  and z - the charges of cation and anion
e is the fundamental charge (1.602  10-9 C
 is a constant (0.35)
re  equlibrium interatomic distance
A is the Madelung Constant
Giving its dependence on large contribution coming from nearest neighbours,
the Madelung constant increases with coordination number

Structure type A Coordination

numbers
ZnS blende 1.638 4, 4

NaCl 1.748 6, 6

CsCl 1.763 8, 8
 The Kapunstinskii Equation

The use of the Born-Landé equation requires the knowledge of the

structure of the compound (Madelung constant)

If the structure of the compound is not known, or the Madelung

constant is not available, the Kapustinskii equation can be used to
calculate the lattice energy

 5
1.214  10   z z  
 34.5  (kJ mol -1 )
U  
1 
r  r  r  r 
 

r  r- (pm) is the sum of the ionic radii (cation - anion distance)

 is the number of ions in the chemical formula
z  and z- are the charges of cation and anion (without the sign)
 Sanderson’s model
- All bonds in non-molecular structure regarded as polar
covalent.

- Atoms contain partial charges whose value maybe calculated

readily using a scale of electronegativities developed by
Sanderson. e.g. KCI, charges on the atoms, + 0.76 in stead of +
1.0 for pure ionic

- Contribution of ionic bonding and covalent bonding to the total

bond energy can be estimated based on the partial charges.

- The physical and chemical properties of an atom are controlled

by:
a. Electronic configuration
b. The effective nuclear charge felt by the valence electron
a) The nuclear effective Charge
- The effective nuclear charge- the positive charge that would be felt
by a foreign electron on arriving at the periphery of the atom.

- The valence electrons – not effective to shield the outside world

from the positive charge on the nucleus. The incoming
electron( from neighbouring atom) feels a positive, attractive
charge.

- If shielded completely- the atom has zero electron affinity and no

bonds, ionic or covalent bond would ever form.

- The effective nuclear charge- more significant in elements which

have a single vacancy in their valance shell. e.g. Halogens
In the inert gases
The outermost electron shell is full and no foreign
electrons can enter.
-the incoming electron would have to occupy the
vacant orbitals which are ‘outside’ the atom and
the effective nuclear charge experienced in such
orbital would be greatly reduced.

Screening constant- suggested by Slater

Outermost electron is less efficient at screening
nuclear charge than electron inner shells.
Screening constant of outmost electron= approx.
one third; means one third of positive charge
screened when unit increase in atomic number
only
• Hence, effective nuclear charge increases in steps two third
and the valence electrons experience an increasingly strong
attraction to the nucleus on going from sodium to chlorine.
• The effective nuclear charge is small for the alkali metals
and increase to a mx in the halogens

Many atomic properties correlate with effective nuclear charge:

From left to right (across periodic table)
1. Ionization potentials increase
2. Electron affinities become increasingly negative
3. Atomic radii decrease
4. Electronegativities increase
b) Atomic radii
Atomic radii vary for a particular atom depending on bond
type and CN and many tabulation of radii are
available( Shannon, Prewitt etc) – still controversial.
Non polar covalent radii can be determined accurately and
represent a point of reference with which to compare
other radii.
e.g. Carbon, given half the C-C single bond length, 0.77 Å
in materials as diverse as diamond and gaseoues
hydrocarbon.
Non polar radii, rc (page 92, West)- used to estimate the
effect that partial charges on atoms have on their radii.
- Partial positive charge increase; the radii become
smaller (valence electron feels stronger attraction from
nucleus as the outmost electrons are removed; the
nuclear charge remain unchanged)
Conversely, with increasing negative charge on the atom, the radius
becomes larger.
Empirical formula developed by Sanderson to quantify the variation of
radius, r with partial charge
r = rc- Bδ
rc- non polar radii
B- constant
δ- Partial charge which can be estimated from Sanderson’s
electronegativities scale
Electronegativity and partial charged atoms
Electronegativity- measure of the net attractive force experienced by an
outmost electron towards the nucleus
Partial charge- ratio of the change in electronegativity undegone by an
atom on bond formation to the change it would have undegone on
becoming completely ionic with charge +1 or -1
Atoms of high electronegativity attract electron > low
electronegativity , acquiring a partial negative charge.

The magnitude of the partial charge depends on the initial

difference in electronegativity between the two atoms.

Bond strength – combination of a homopolar bond energy and

‘extra ionic energy’ due to the bond polarity, hence
electronegativity difference.

Electronegativity – measure of the attraction between the

effective nuclear charge and an outermost electron-
compactness of an atom.

S= D/Da
D - electron density of the atom (ration of atomic number: atomic
volume)
Da – E.D expected for the atom by linear interpolation of the D
values for the inert gas elements.
The principle of electronegativity equalization-
when two or more atoms initially different in
electronegativity combine chemically, they
adjust to have the same intermediate
electronegativity within the compound.
e.g. NaF, the intermediate electronegativity is
given by the geometrical mean of the individual
electronegativities of the component atoms.
Sb= √SNaSF= 2.006
The bonding electrons are preferentially and
partially transfer to from the less electronegative
to the most electronegative
 Bond valence and bond length
The bond valence sum of each ion should equal its oxidation state.

This idea is well known in organic chemistry where each bond has a
valence of 1. So that C always has a valence sum of 4 (4 bonds), O always
forms 2 bonds, H forms 1 bond, etc.

For inorganic compounds, Pauling’s proposed that the valence of a

bond, sij, could be non-integer, and the sum of the bond valences
around
each atom, should equal its oxidation state.
Vi = Σ sij

Vi = The oxidation state of atom i

sij = The valence of the bond between atoms i and j.

If there are n equivalent bonds around a central atom with valence m,

then valence of each bond is equal to:
sij = m/n.
Consider the rutile form of TiO2. What is the valence of
the Ti-O bonds?
First lets calculate the valence of the Ti-O bonds.
Vi = Σ sij
4 = 6(sij)
sij = 2/3
Hence, the coordination number of oxygen.

Vi = Σ sij
2 = n(2/3)
n=3
The presence of shared edges and particularly shared
faces decreases the stability of a structure- cations with
large valences and small coordination number.

When polyhedra share a common edge or face- cations are

getting closer together, electrostatic repulsions will
increase
In a crystal containing different cations, those with large valence and small
coordination number tend not to share polyhedron elements with each
other.

This aroused from bonding preferences of the anion. e.g.

CaWO4 has the scheelite structure where the W+6 ions are tetrahedrally
coordinated.

The valence of the W-O bond is:

Vi = Σ sij
6 = 4(sW-O) sW-O = 1.5

If a proposed structure where two WO4 tetrahedra shared a corner, the shared
oxygen would be bound to 2 W+6 ions. Its valence is:

VO = 2 sW-O
VO = 2(1.5) = 3

This is against rule which bond valence sum equals to oxidation sate.

This effect is exacerbated as the cation valence increases its coordination number
decreases, because sij increases.