Crystallography - Solid Materials

Rajshahi University of Engineering & Technology
Department of Glass & Ceramic Engineering
Online class
on
Course no : GCE2103
Course Title : Crystallography
Lecture-3
Topic- Solid Materials Prepared by
Shamima Akhter Urmi
Lecturer, Dept. of GCE,
RUET
Shamima Akhter Urmi, Lecturer, GCE
Types of Solids
Self Study
Structure
Properties
Applications
Types of Solids : Polycrystalline solid
Bonding in Solids
 Bond: A bond may be defined as a force that holds groups of two or more atoms together, causing
them to behave as a single unit.
 The process of holding these atoms, ions or molecules together is known as bonding in solids
 Bonds can be separated into two types:
1. primary bonds and
2. secondary bonds
 Primary bonds are formed when the bonding process involves a transfer or sharing of electrons.
 Secondary bonds are formed from the subtle attraction forces between positive and negative
charges. There is no transfer or sharing of electrons involved in a secondary bond.
 Bond Energy
Bond energy is the measure of bond strength. In order to turn one mole of a molecule into its
constituent atoms, an amount of heat equal to the bond energy needs to be put into the system.
Types of Crystalline Solids
Bonding in Solids : Van der Waals bonding
• Van der Waals bonds are a result of an asymmetrical distribution of positive and negative charges
inside each atom or molecule, which creates in a dipole.
• A temporary dipole is induced upon a normally symmetric atom/molecule due to external charges
from another atom/molecule.
• The presence of these external charges causes a slight distortion of the symmetric charge, therefore
creating areas that are more positive or more negative than others. Two such distorted
atoms/molecules can feel a relatively small attraction to one another because of these induced
dipoles. This results in a van der Waals bond.
• Conversely, a permanent dipole occurs when the shape of the molecule is already asymmetric
causing permanent separation of charge. This results in a large dipole moment and greater
attraction (although still relatively weak).
Bonding in Solids : Molecular solid & Hydrogen
bonding
 Hydrogen bonding, interaction involving a hydrogen atom located between a pair of other atoms
having a high affinity for electrons; such a bond is weaker than an ionic bond or covalent bond but
stronger than van der Waals forces. Hydrogen bonds can exist between atoms in different
molecules or in parts of the same molecule.
Primary Bond Vs Secondary Bond
Isomorphism
• When two or more crystals have similar chemical composition exist in the same crystalline form,
this property is called isomorphism.
• And these substances are known as Isomorphous.
• Have same atomic ratio.
• Examples: 1) Na2SO4 Ag2SO4 both exist in HCP crystalline form.
2) KBF4 BaSO4 -Orthorhombic
3) ZnSO4 NiSO4 -Orthorhombic
4) CaCO3 NaNO3 -Trigonal
Polymorphism
 Polymorphism comes from the Greek word, Polus means many and morph means shape.
 When a particular substance exists in more than one crystalline form, the property is called
polymorphism.
 e.g. Calcium carbonate exists in two crystalline forms called calcite and aragonite.
 When this phenomenon is found in elemental solids, this is known as allotropy.
 e.g. graphite and diamond are two polymorphs of carbon. Graphite is stable at ambient conditions,
whereas diamond is formed at extremely high pressure.
Enantiotropy & Monotropy
• Polymorphs are categorized into 2 types:
1. Enantiotropy
2. Monotropy
Isomorphism Vs Polymorphism
Cohesive energy of ionic crystals
The amount of energy required to pull the crystal apart into a set of free atoms is
called the cohesive energy of the crystal.
Cohesive energy = Energy of free atom— Crystal energy

Cohesive energy of ionic crystals
Lattice energy of ionic crystals
• The energy required to break an ionic solid and convert its component atoms into
gaseous ions.
• Endothermic reaction (+ve)
• The energy released when gaseous ions bind to form an ionic soid.
• Exothermic reaction (-ve)
Born-Haber Cycle
• Born-Haber cycle is an approach of analyzing reaction energies.
• Developed by two German scientist Max Born and Frit Haber.
• Hess’ Law:
This law states that the overall change in energy of a process can be
determined by breaking the process down into steps, then adding the
changes in energy of each step.
Important terms in Born-Haber Cycle
• Ionization energy
• Electron Affinity
• Dissociation energy
• Sublimation energy
• Heat of formation
Born-Haber Cycle

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Cohesive energy = Energy of free atom— Crystal energy

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Crystallography - Solid Materials

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Crystallography - Solid Materials

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Department of Glass & Ceramic Engineering

Cohesive energy = Energy of free atom­— Crystal energy

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Cohesive energy = Energy of free atom— Crystal energy