CHM 102 Lecture notes

STRUCTURE OF SOLIDS

Dr. O.M. Bankole

Solids: Solids are the chemical substances which are characterised by definite

shape volume, rigidity, high density, and low compressibility. The constituent

particles (atoms, molecules or ions) are closely packed and held together by

strong interparticle forces

Types of Solids

A. Crystalline solids

B. Amorphous solids.

Distinction Between Crystalline and Amorphous Solids

Crystalline solid Amorphous solids

They have definite and regular No regular arrangement of

arrangement of the constituent particles the constituent particles

They are true solids They are super cooled liquids or

pseudo solids

They have long order arrangement of the They have short order

particles arrangement of particles

They are anisotropic in nature, i.e., their They are isotropic in nature i.e.,

physical properties are different in their physical properties are same

different directions in all the directions

They have sharp melting points They melt over a certain range of

temperature

They undergo a clean cleavage when cut They undergo irregular cleavage

when cut
 Types of Crystalline Solids

Character Ionic Solids Covalent Molecular Solids Metallic Solids

Solids

Constituent Positive and Atoms Molecules Positive metals and

particles negative ions free electrons

Bonding Electrostatic Covalent Van der Waal’s, Electrostatic

forces attraction Dipole-dipole attraction

Melting High melting Very high Low melting point Moderate to high

point point melting melting point

point

Solid Structure Determination by X-ray Diffraction (XRD)

XRD is a non-destructive method for determination of solid samples. When a

beam of X-rays falls on a crystal plane composed of regularly arranged atoms or

ions, the X-rays are diffracted. If the waves are in phase after reflection, the

difference in distance travelled by the two rays i.e., path difference) must be

equal to an integral number of wavelength, 𝒏𝝀.

Thus, path difference = WY + YZ

𝑊𝑦 𝑦𝑍
sin 𝜃 = 𝑎𝑛𝑑 𝑎𝑙𝑠𝑜, sin 𝜃 =
𝑥𝑦 𝑥𝑦

𝑊𝑦 = 𝑥𝑦 𝑠𝑖𝑛 𝜃 and 𝑦𝑍 = 𝑥𝑦 𝑠𝑖𝑛 𝜃

𝑊𝑦 + 𝑦𝑍 = 𝑥𝑦 𝑠𝑖𝑛 𝜃 + 𝑥𝑦 𝑠𝑖𝑛 𝜃 = 2 𝑥𝑦 𝑠𝑖𝑛 𝜃 = 2𝑑 𝑠𝑖𝑛 𝜃
∴ 𝑛𝝀 = 𝟐𝒅 𝒔𝒊𝒏 𝜽 This is called Bragg’s equation.
Where, n = 1. 2, 3… (diffraction order)

λ = wavelength of X·rays incident on crystal

d = distance between atomic planes

𝜃 = angle at which interference occurs.

Lattices and Unit Cell

Lattice: This is defined as array of points in space where objects are replaced by
imaginary points.

Unit Cell: The smallest geometrical portion of the crystal lattice which can be

used as repetitive unit to build up the whole crystal is called unit cell. A unit cell is
characterized by six parameters. These parameters are three edges (a, b and c) and angles
between them (α, β and γ)
Types of Unit Cell

1. Simple cubic unit cell: In which the particles are present at the corners
only. Example is polonium (Po).
2. Face centred unit (fcc) cell: In which the particles are present at the corners
as well as at the centre of each of six faces, example is Iron (Fe).

3. Body centred unit (bcc) cell: In which the particles are present at the
corners as well as at the centre of the unit cell. Example is Gold (Au)

Number of Particles Per Unit Cell

Counting the number of atoms within the unit cell, others atoms within

the unit cell are equally shared.

 Unit cell No. of particles and their contribution Total

Corner Face Centre

Simple cubic 8 × 1/8 - - 1

Face centred 8 × 1/8 6 × 1/2 - 4

Body centred 8 × 1/8 - 1 2

Seven Crystal Systems

There are about 230 crystal forms, which have been grouped into 14 types of

space lattices, called Bravais Lattices, on the basis of their symmetry and

seven different crystal systems on the basis of interfacial angles and axes.

Crystal system Parameters of unit cell Types of Lattices

Intercept/axes Angles

Cubic 𝑎=𝑏=𝑐 𝛼 = 𝛽 = 𝛾 = 90° Simple cubic, Face

centered, Body centred

Tetragonal 𝑎=𝑏≠𝑐 𝛼 = 𝛽 = 𝛾 = 90° Simple cubic, Body

centred

Rhombohedral 𝑎=𝑏=𝑐 𝛼 = 𝛽 = 𝛾 ≠ 90° Simple cubic

Orthorhombic 𝑎≠𝑏≠𝑐 𝛼 = 𝛽 = 𝛾 = 90° Simple cubic, Face

centered, Body

centred, End centered

 Monoclinic 𝑎≠𝑏≠𝑐 𝛼 = 𝛾 = 90°, 𝛽 Simple cubic, End
≠ 90° centered

Triclinic 𝑎≠𝑏≠𝑐 𝛼 ≠ 𝛽 ≠ 𝛾 ≠ 90° Simple cubic

Hexagonal 𝑎=𝑏≠𝑐 𝛼 = 𝛽 = 90°, Simple cubic

𝛾 = 120°
Note; the 14 types of Lattices are collectively referred to as Bravais Lattices.

Packing Fraction (PF)

Packing Fraction is defined as the ratio of the volume of atom in unit cell that is

occupied by the spheres to the total volume of the unit cell.

A. Simple cubic unit cell: atoms touch each other along the edges such that

𝒅 = 𝒂 or 𝒓 = 𝒂/𝟐 (r = radius of atom and a = edge length)

𝟒
Volume of atom in unit cell = 𝝅𝒓𝟑 ,
𝟑

Total volume of unit cell = 𝒂𝟑 = (𝟐𝒓𝟑 )

𝟒
𝝅𝒓𝟑
Therefore, PF = 𝟑
(𝟐𝒓𝟑 )
= 𝟎. 𝟓𝟐𝟒

Also, %𝑷𝑭 = 𝟓𝟐. 𝟒%

B. Face centred cubic unit cell: atoms touch each other along the face

diagonal such that

d = 𝒂/√𝟐 or r = √2a/4
𝟒
Volume of atom in fcc = 𝟒(𝟑 𝝅𝒓𝟑 ) ,
𝟒𝒓
Total volume of unit cell = 𝒂𝟑 = ( )𝒓𝟑
√𝟐
𝟒
𝟒( 𝝅𝒓𝟑 )
Therefore, PF = 𝟑
𝟒𝒓 = 𝟎. 𝟕𝟒
( )𝒓𝟑
√𝟐

Also, %𝑷𝑭 = 𝟕𝟒%

C. Body centred cubic unit cell Atoms touch each other along the body

diagonal such that

𝑑 = √3a/2 or r = √3a/4
𝟒
Volume of atom in fcc = 𝟐(𝟑 𝝅𝒓𝟑 ) ,
 𝟒𝒓
Total volume of unit cell = 𝒂𝟑 = ( )𝒓𝟑
√𝟑
𝟒
𝟐( 𝝅𝒓𝟑 )
Therefore, PF = 𝟑
𝟒𝒓 = 𝟎. 𝟔𝟖
( )𝒓𝟑
√𝟑

Also, %𝑷𝑭 = 𝟔𝟖%

Coordination Number (CN)

It is defined as the number of particles immediately adjacent to each particle

in the crystal lattice.

A. Simple cubic lattice has 6 CN

B. Body centred lattice has 8 CN

C. Face centred cubic lattice has 12 CN

NOTE: High pressure increases CN and high temperature decreases the CN.

Density of Unit Cell (𝝆)

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Density of unit cell (𝜌) =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝑍𝑀
(𝜌) =
𝑁𝐴 𝑉𝐶

𝑍 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

𝑀 = 𝑎𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡

𝑁𝐴 = 𝐴𝑣𝑜𝑔𝑎𝑑𝑟𝑜’𝑠 𝑛𝑢𝑚𝑏𝑒𝑟

𝑉𝐶 = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎3

Magnetic Properties of Solids

Solids can be divided into different classes depending on their response to

magnetic field.

A. Diamagnetic Substances: these are solids that are weakly repelled by

the magnetic field and do not have any unpaired electrons, e.g., TiO2,

V2O5, C6H6, NaCl, etc.

B. Paramagnetic Substances: these are solids that are attracted by the

magnetic field and have unpaired electrons They lose their magnetism in

the absence of magnetic field, e.g., O2, Cu2+, Fe3+, etc.

C. Ferromagnetic Substances: these solids are attracted by the magnetic

field and show permanent magnetism even in the absence of magnetic

fields e.g., Fe, Co and Ni.