Solid State
Chemistry for Engineers
SOLIDS
Definite shape and volume
Highly incompressible and rigid
High mechanical strength
Sharp melting point
Characteristics heat of fusion
Definite 3D arrangement
Types of Solids
Crystalline vs Amorphous
▪ Particles have regular ▪ Random arrangement of the
arrangement particles
▪ Long – range order ▪ Short – range order
▪ Sharp melting point ▪ Generally melt over a range of
temperature
▪ Cleaved among definite planes ▪ Undergo irregular breakage
▪ Different physical properties in ▪ Physical properties identical in all
different direction directions in any axis
▪ Cooling curves have two breakes ▪ Cooling curve is smooth
▪ Common example: NaCl, KCl, ▪ Common example: glass, plastics
sugar, diamond and polymers
Classes of Solids
▪ Molecular solids
Molecules are the structural units
Held together by van der Waals forces
Other forces: hydrogen bonds, london
dispersion forces and dipole–dipole interactions
Poor thermal and electrical conduction
Example: solid carbon dioxide, ice and iodine
Classes of Solids
▪ Ionic solids
Made of positively and negatively charged ions
arranged in a regular fashion throughout the
crystal and are held together by strong
electrostatic forces of attraction
hard, brittle and have high melting and boiling
points
Example: NaCl, KCl, NaNO3, LiF and Na2SO4.
Classes of Solids
▪ Covalent solids
made up of atoms that are bonded together by
covalent bonds
atoms are interlinked by covalent linkages to
form giant network solids
High melting points; poor thermal and electrical
conductivity
Example: diamond, silicon carbide, quartz and
silica
Classes of Solids
▪ Metallic solids
constituent particles are positive kernels
immersed in a sea of mobile electrons
Forces of attraction: metallic bonds
High melting and boiling point
Good conductors of heat and electricity
soft to very hard and are malleable and ductile
Example: Cu, Fe, Al and Ni
Crystal Lattice and Unit Cell
Crystal lattice
• a regular and repeating arrangement of
particles (atoms, ions or molecules) in three-
dimensional space
Lattice points (sites)
• positions occupied by the particles in this
three dimensional arrangement
Unit Cell
• smallest portion of a crystal (space) lattice
which produces the complete space lattice
by repeating itself again and again
To describe a lattice cell,
▪ Length of edges (a, b, c)
▪ Angles (𝛼, 𝛽 and 𝛾)
between the edges a and
b, c and b, and a and c
respectively
Crystal Systems (Bravis Lattice)
Types of Unit Cells
Packing of Crystals
Close Packing – a type of packing in which the
constituent particles (atoms, ions or molecules) get
closely packed together in such a way that they occupy
the maximum available space
Coordination Number – the number of atoms (spheres)
touching a given sphere
Note: in packing, all the spheres are of equal size
Properties of different packing of
Crystals
Interstitial Sites or Voids
1. Tetrahedral Void
2. Octahedral Void
Coordination Number and Radius Ratio
Radius Ratio
▪ The ratio of the radius of the cation to the radius of the
anion
𝑟𝑎𝑑𝑖𝑢𝑠 𝑜𝑓 𝑐𝑎𝑡𝑖𝑜𝑛 𝑟 +
𝑅𝑎𝑑𝑖𝑢𝑠 𝑅𝑎𝑡𝑖𝑜 = = −
𝑟𝑎𝑑𝑖𝑢𝑠 𝑜𝑓 𝑎𝑛𝑖𝑜𝑛 𝑟
Effects of Radius Ratio on Coordination
Number
Example
The radii of two ions X+ and Y– are 90 and 204 pm,
respectively. In the close packed crystal of the
compound XY, predict the coordination number of X+.
Example
The radii of Zn2+ and S2– ions are 74 and 184 pm,
respectively. Predict the probable type of
coordination of Zn2+ ions.
Example
A solid AB crystallizes into an NaCl type
structure. If the radius of cation A is 100 pm,
what is the radius of anion B?
Packing Efficiency and Atomic Radius
▪ Packing Efficiency - the percentage or fraction of
the total volume occupied by the particles (spheres)
in a crystal lattice.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑠𝑝ℎ𝑒𝑟𝑒
𝑃𝑎𝑐𝑘𝑖𝑛𝑔 𝐹𝑎𝑐𝑡𝑜𝑟 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓𝑡ℎ𝑒 𝑐𝑢𝑏𝑒
Simple cubic unit cell
a = 2r
r = a/2
Where:
a = edge length of unit cell
r = radius of the sphere
Number of sphere per unit cell = 4
Face Centered Cubic (FCC) / Cubic Close
Packing (CCP)
4𝑟
𝑎=
2
𝑎
𝑟=
2 2
Number of spheres per unit cell = 4
Body centered cubic (BCC) arrangement
𝑟=𝑎 3 4
4𝑟
𝑎=
3
No. of sphere per unit cell = 2
Example
Iron crystallizes into a body centered
cubic structure. Calculate the radius of
an iron atom if the edge length of a
unit cell is 286 pm.
Example
Xenon crystallizes into a face centered cubic
lattice. The edge of the unit cell is 620 pm. Find
the distance with the nearest neighbor and
radius of the xenon atom.
Example:
NH4Cl crystallizes into a body centered cubic lattice.
It has an edge length of 400 pm. Calculate:
(a)Distance between NH4+ and Cl–, that is, the
oppositely charged ions in the lattice.
(b)If the radius of NH4+ ions is 160 pm, find the radius
of Cl– ion.
Crystal Density
Edge length = a 𝑝𝑚 = 𝑎 𝑥10−10 𝑐𝑚 = 𝑎 𝑥 10−12 𝑚
Volume of unit cell = (𝑎 𝑥 10−10 𝑐𝑚)3 = 𝑎3 𝑥103 𝑐𝑚
Density of unit cell = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Mass of unit cell = no. of atoms in unit cell (z) x mass of each atom (m)
𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 (𝑀)
Mass of each atom (m) = 𝑎𝑣𝑜𝑔𝑎𝑑𝑟𝑜′ 𝑠 𝑛𝑢𝑚𝑏𝑒𝑟 (𝑁 )
𝑜
𝑧𝑀
Density of Unit Cell (𝜌) = 𝑁 (𝑎3 𝑥10−30 ) 𝑔/𝑐𝑐
0
Example
Chromium has a monoatomic body centered cubic
structure with an edge length of 300 pm.
Calculate its density if the molar mass of Cr = 52 g / mol.
Avogadro number = N0 = 6.023 × 1023 per mole.
Example
Sodium has a BCC structure with nearest
neighbor distance 365.9 pm. Calculate its
density (atomic mass of sodium = 23)
Imperfection of Solids
i. Electronic imperfection
▪ defects in ionic crystals due to electrons
i. Atomic imperfections
▪ also termed as point defects and arise due to
irregularity in the arrangement of atoms or ions in the
crystal
End of Chapter 3
Good Luck on your Midterm Exam
