Chapter 5: Solid State Chemistry

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 Collection of natural crystals
(I) Halite NaCI; (2) calcite CaCO3; (3) beryl Be3AI2 [Si6O18];
(II) (4) vorobievite, a pink variety of beryl; (5) emerald, a bright-green Small single crystal
variety of beryl; (6) pyrite FeS2; (7) quartz SiO2

Collection of synthetic single crystals

(l, 2) quartz SiO2; (4) potassium dihydrophosphate

KH2PO4; (5) lithium fluoride LiF; (6) lithium iodate LiIO3 ;

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 • Crystal structure is a unique arrangement of atoms, molecules or
ions constructed by the infinite repetition of identical structural units
in space
Lattice Crystal
Translationally periodic Translationally periodic
arrangement of points arrangement of motifs

Crystal = Lattice + Motif

Lattice  the underlying periodicity of the crystal,
Basis or Motif  atom or group of atoms associated with each lattice points

Lattice  how to repeat

Motif or basis  what to repeat

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 Lattices
• A lattice is a regular infinite arrangement of points in which every
point has the same environment as any other point.
• A lattice in 2 dimensions is called a net and a regular stacking of
nets gives us a 3-dimensional lattice.

2-D net Stacks of 2-D nets produce 3-D lattices

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• The lattice can be considered as a kind of scaffold upon which the
structure of the crystal is built.
• The corners of the unit cell therefore serve as points which are
repeated to form a lattice array; these points are termed lattice
points.
• The vectors which connect a straight line of equivalent lattice points
and delineate the edges of the unit cell are known as the
crystallographic axes.

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• The smallest repeating unit that will generate the entire lattice (by
translation) is called the Unit Cell.
• It is defined by three repeat distances (a, b, and c) and three angles
(a, b, g), where a is the angle between b and c, b is the angle
between a and c, and g is the angle between a and b.

Unit cell parameters (a, b, c, a, b, g) are chosen to best represent the

highest-possible symmetry of the crystal and are given right-handed
axes (a is along x, b is along y and c is along z) with angles that are
either all ≥ 90º or all ≤ 90º.
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 Types of Solids
Ionic Crystals or Solids
• Lattice points occupied by cations and anions
• Held together by electrostatic attraction
• Hard, brittle, high melting point
• Poor conductor of heat and electricity

CsCl ZnS CaF2

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Molecular Crystals or Solids
• Lattice points occupied by molecules
• Held together by intermolecular forces
• Soft, low melting point
• Poor conductor of heat and electricity

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Network or covalent Crystals or Solids
• Lattice points occupied by atoms
• Held together by covalent bonds
• Hard, high melting point
• Poor conductor of heat and electricity
carbon
atoms

diamond graphite
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Metallic Crystals or Solids
• Lattice points occupied by metal atoms
• Held together by metallic bond
• Soft to hard, low to high melting point
• Good conductor of heat and electricity
Cross Section of a Metallic Crystal
nucleus &
inner shell e-

mobile “sea”
of e-

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 Cont…
• Bravais lattices : The space lattices which are invariant under one or more
point of the symmetry operation are known as Bravais lattices. There are
14 unique Bravais lattices in three dimensions
Triclinic - 1 Bravais Lattice, least symmetric

 Monoclinic – 2 Bravais Lattices

 Orthorhombic – 4 Bravais Lattices

 Rhombohedral/Trigonal -1 Bravais Lattice

 Tetragonal – 2 Bravais Lattices

 Hexagonal – 1 Bravais Lattices

 Cubic - 3 Bravais Lattices, most symmetric

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 CLOSE PACKING
• In order to understand the packing of atoms molecules or ions in crystals,
let us consider the packing of hard spheres of equal size in two
dimensions, in a layer and to extend the arrangement to three dimensions
by putting such layers above one another.
• There are two common ways of packing spheres of equal size in a layer.

Arrangement I Arrangement II

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 Cont…

• A comparison of the two ways of packing of spheres shows that in

arrangement I, the spheres are more closely packed i.e., about 60.4% the
volume is occupied. The remaining 39.6% of the space is empty and is
called void volume.
• In arrange II, only 52.4% of the volume is occupied

• Many crystal structures originate from arrangement of atoms that

maximize the density (ie. minimize empty space or void volume)

• The closer the packing, the greater is the stability of the packed system.

• There are two ways of packing spheres to maximize the density.

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 Cont…
• Hexagonal close packing (HCP)- A hexagonal structure having the
maximum coordination number of 12 formed by stacking atoms in
repeating patterns ABABAB
• Cubic close packing (CCP) – a face centered cubic structure having a
maximum coordination number of 12 formed by stacking atoms in layers
having the repeating pattern ABCABCABC

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 HCP and CCP

HCP CCP

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1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell
(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)

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Cont…

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 Holes in close packed crystals

• There are two types of holes created by a close-packed arrangement.

• Octahedral holes lie within two staggered triangular planes of atoms.
The coordination number of an atom occupying an octahedral hole is
6.
• For n atoms in a close-packed structure, there are n octahedral holes

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 Cont…
• Tetrahedral holes are formed by a planar triangle of atoms, with a
4th atom covering the indentation in the center. The resulting hole
has a coordination number of 4

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 Ionic Radii
• Ionic radii increase as you go down a group.

• Radii of ions of similar charge decrease across a period

• If an ion can be found in many environments, its radius

increases with higher coordination number.

• For cations, the greater the charge, the smaller the ion
(assuming the same coordination #).

• For atoms near each other on the periodic table,

cations are generally smaller than anions
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 Limiting Radius Ratio
• X-ray studies show that in ionic solids, positive ions are surrounded
by negative ions, and vice versa.

• The structure of ionic compounds depends on relative sizes of the

cations and anions concerned.

• If for example, anions are larger, they form close packed

arrangement and the cations just fit into (occupy) the resulting
interstitial sites of tetrahedral or octahedral type.

• Some of the coordination numbers and their limiting radius ratios

are given in the table below

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 Limiting radius ratio for trigonal site

• Let r+ and r- be the radii of cation and anion

• From above equilateral triangle, EBC

•BC = CE = BE = 2r-

• If A is the centre of the triangle ( and hence of

ther cation)

r then

r 
 1 ( )
BD r = r- r and AB = r+ + r-
 

r 2
( 
)  1  0.155
r 3
In the right angled triangle, BDA ,
cos <ABD = BD/AB = cos 300 = r
(r   r  )
3 r
Since cos30 = 2
=
(r   r  )
2 r  r r
 1 (  )
on inverting both sides, 3 = r  r
r 2
( )  1  0.155
r 3
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Cont…

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Classification of crystal structure

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 Rock-salt structure
• Sodium chloride NaCl is a typical compound in which Cl- anions are
arranged in ccp and Na+ cations occupy all the octahedral holes (Oh
holes).
• Each Na+ cation is surrounded by six Cl- anions.
• The same structure results even if the positions of anions and
cations are exchanged

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 Cesium chloride structure
• Cesium chloride, CsCl, is a typical example of the structure
• There is a Cs+ ion at the center and eight Cl- are located at the eight
corners of the cube
• Conversely, even if a Cl- comes to the center and eight Cs+ come to the
corners, the number of each ion in the unit lattice is the same
• Thus, this is referred to as the (8, 8)-structure. Since there is one Cs+
and one Cl- ion belonging to this unit lattice, it coincides with the
formula CsCl

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 Zinc blende structure
• Zinc blende has the composition ZnS
• S2- anions are arranged in ccp and Zn2+ cations occupy half of the
tetrahedral holes (Td holes).
• In this arrangement, each cation is coordinated by four anions, and each
anion by four cations.
• Hence, this is a (4, 4)-structure. There are both four Zn2+ and S2- ions
belonging to this unit lattice and the atomic ratio coincides with the
formula of ZnS

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