Course: CHEM 1101

Introduction to Physical Chemistry

(3 Credits)

Chapter- 4
Mohy Menul Islam
Lecturer
Department of Chemistry Department of Chemistry
First Year, First Semester
Sunamgonj Science and Technology University
Session: 2023-24
E-mail: mohymenul@[Link]
21/01/2025 Homepage: [Link]
The Solid State: Molecular interpretation, classification of solids (ionic,
covalent, metallic or molecular), crystalline, amorphous solids, types of
crystalline solids (ideal, ideally imperfect, imperfect), isomorphism,
polymorphism, allotropy. Crystal lattice, unit cell, elementary idea on crystal
systems.

References
1. Principles of Physical Chemistry, M. M. Huque and M. Yousuf Ali Mollah
2. Physical Chemistry, P. Atkins and J.D Paula
3. Solid State Chemistry and its Applications, A. R. West
4. Essentials of Physical Chemistry, A. Bahl, B.S. Bahl, and [Link]
5. Solid State- Wikipedia
6. Solid State- Britannica
7. Solid- [Link]
 Characteristics
Solid
 Definite Shape and Volume: Solids have a fixed shape and volume. This is
because their constituent particles (atoms, ions, or molecules) are tightly packed
together, leaving little space for movement.

 Intermolecular Forces: The strength of intermolecular forces in solids is generally

high. These forces hold the particles together and give solids their characteristic
properties.

 Rigidity and Incompressibility: Solids are rigid and incompressible due to the
strong intermolecular forces between their particles. This makes it difficult to
change their shape or volume.
 Characteristics
Solid
 High Density: Solids have a high density because their particles are closely packed
together. This means that a large amount of matter is packed into a small volume.

 Low Kinetic Energy: The particles in solids have very low kinetic energy, which
means they vibrate about their fixed positions but do not move freely. This low
kinetic energy contributes to the rigidity and stability of solids.

 Low Diffusion Rate: The diffusion rate of particles in solids is very low. This is
because the particles are tightly bound and have limited mobility.
The Solid State

 Solids are characterized by their definite shapes and fixed volumes.

The rigid structure indicates that strong forces of attraction hold
together the atoms, molecules, or ions in solids, and the constituents
are placed in fixed positions from which they can not move
appreciably.
 As a result, the solid substances assume rigidity and mechanical
strength and have definite shapes.
 The forces holding the constituent atoms, molecules, or ions are
different and give rise to differences in the physical properties of the
solids.
The Solid State
Solid is one of the three major states of matter. It is characterized by structural
rigidity and resistance to changes of shape or volume. In the solid state, attractive
forces predominate. They confine atoms, molecules and ions to fixed positions, and
they limit their motions to a mere jiggling in place.

Based on the nature of the forces that hold the component atoms,
molecules, or ions together, solids may be formally classified as
(i) Ionic Solid
(ii) Covalent Solid
(iii) Metallic Solid
(iv) Molecular Solid
The Solid State
(i) Ionic solids: An ionic solid is a solid that consists of cations and anions held
together by the electrical attraction of opposite charges (ionic bonds). Ionic
solids are formed between highly electropositive and electronegative elements when
electron transfer has occurred between the atoms.
Examples are NaCl, KCl, CaS, etc.
The strength of the attractive forces depends on the charge and size of the ions that
compose the lattice and determines many of the physical properties of the crystal.
NaCl
The Solid State
(ii) Covalent solids: A covalent solid is a solid that consists of atoms held
together in large networks or chains by covalent bonds. Covalent solids are formed
when elements have similar electronegativity. Sharing of electrons and overlap of
atomic orbitals take place.
Examples: SiC and diamond. Because all of the bonds in this structure are equally
strong, covalent solids are often very hard and they are notoriously difficult to melt.
Diamond is the hardest natural substance and it melts at 3550 oC.
Diamond
The Solid State
(iii) Metallic solids: A metallic solid is a solid that consists of positive cores of
atoms held together by a surrounding sea of electrons. Outer electrons of metal atoms
are free to move resulting in high electrical and thermal conductivity.
Example: almost all metals and their alloys, such as gold, brass, steel, etc.
The Solid State
(iv) Molecular solids: Molecular solids consist of molecules held to each other
by dipole-dipole interactions, London dispersion forces, or hydrogen bonds, or
any combination of these. Because the intermolecular interactions in a molecular
solid are relatively weak compared with ionic and covalent bonds, molecular solids
tend to be soft, low melting, and easily vaporized.
Examples of molecular solids include hydrocarbons, ice, sugar, fullerenes, sulfur and
solid carbon dioxide.

Dry ice, or frozen carbon dioxide

The Solid State

Ionic solids Covalent solids Metallic solids Molecular solids

Poor conductors of heat Poor conductors of heat Good conductor of heat and Poor conductors of heat
and electricity and electricity* electricity and electricity
Relatively high melting High melting point Melting points depends strongly Low melting point
point on electron configuration

Hard but brittle; shatter Very hard and brittle Easily deformed under stress; Soft
under stress ductile and malleable

Relatively dense Low density Usually high density Low density

Dull surface Dull surface Lustrous Dull surface

*Many exceptions exist. For example, graphite has a relatively high electrical conductivity within the carbon
planes, and diamond has the highest thermal conductivity of any known substance.
The Solid State
Solid is one of the three major states of matter. It is characterized by structural
rigidity and resistance to changes of shape or volume. In the solid state, attractive
forces predominate. They confine atoms, molecules and ions to fixed positions, and
they limit their motions to a mere jiggling in place.

From a structural point of view, crystalline solids are of three distinct

types:
(i) Ideal crystals
(ii) Ideally imperfect crystals
(iii) Imperfect crystals
The Solid State
(i) Ideal crystals: Have a very high degree of internal order, in other words, the
lattice arrays of atoms, molecules or ions persist without flaws in all directions in the
crystal. Ideal crystal does not really exist. For an ideal crystal,
I ∞ F (where, I = intensity, F = structure factor).
The Solid State
(ii) Ideally imperfect crystals: Lattice arrays of objects (atoms, molecules or
ions) are not continuous throughout the crystals but are broken up into blocks by
discontinuities at the block boundaries. It is like a mosaic in which each part is perfect
but tipped slightly relative to its neighbors. An ideally imperfect crystal is also not an
accurate representation of crystals existing in nature. For an ideally imperfect crystal,
I ∞ Fm (where, I = intensity, F = structure factor, m =1 - 2)
The Solid State
(iii) Imperfect crystals: Having large deviation from a highly ordered
arrangement of atoms, molecules or ions. Most of the naturally occurring crystals are
imperfect. For an imperfect crystal,
I ∞ F2 (where, I = intensity, F = structure factor)
Isomorphism: When two or more crystalline substances have the same number of
atoms and the same shape (crystalline form), the phenomenon is called isomorphism
and such substances are said to be isomorphous substances with each other. For
example, ZnSO4.7H2O and FeSO4.7H2O are isomorphous with each other.
As2O3 Sb2O3

Rhombic form Octahedral form Rhombic form Octahedral form

Polymorphous forms Polymorphous forms

Isomorphous forms
Isomorphous forms

Polymorphism: The phenomenon by which a substance exists in two or more

different crystalline forms is called polymorphism and the different crystalline forms
are said to be polymorphous with each other. For example, As 2O3 (or Sb2O3) exists in
two polymorphic forms: rhombic and octahedral. These two forms are said to be
polymorphous with each other.
Allotropy: Different crystalline forms of the same element are called its allotropes
or allotropic forms and the phenomenon is called allotropy. For example, different
crystalline forms of sulphur, rhombic sulphur or α-sulphur and monoclinic sulphur or
β-sulphur are allotropes of each other.

α-sulphur
β-sulphur
The Solid State
Solid is one of the three major states of matter. It is characterized by structural
rigidity and resistance to changes of shape or volume. In the solid state, attractive
forces predominate. They confine atoms, molecules and ions to fixed positions, and
they limit their motions to a mere jiggling in place.

From a structural viewpoint, solids can be divided into two distinct

classes:
(i) Crystalline Solid
(ii) Amorphous Solid
Crystalline Solid Atoms, ions or molecules

 A crystalline solid is a solid material,

whose constituent atoms, molecules, or
ions are arranged in an orderly
repeating pattern extending in all three
spatial dimensions.
 Some common examples of crystalline
solids are sodium chloride, sulphur,
diamond, sugar, etc. About 95% of all
solids can be described as crystalline.
Amorphous Solid

 An amorphous solid is a solid in which

there is no long-range order or repeating
pattern in the positions of its atoms or
molecules.
 The common examples of amorphous solids Atoms, ions or molecules
are glass, rubber, fused silica, plastics, etc.
 Crystalline Solids Vs Amorphous Solids
Crystalline Solids Amorphous Solids
1. They have a definite geometrical shape due to finite and orderly 1. They do not have any orderly pattern of arrangement
arrangement of particles in three-dimensions. of particles and, therefore, do not have any definite
geometrical shape.
2. Crystalline solids have crystal symmetry i.e., when a crystalline 2. Amorphous solids do not have symmetry.
solid is rotated about an axis, its appearance does not change.
3. The melting point of crystalline solids is finite. 3. Amorphous solids don't have particular melting
point. They melt over a wide range of temperature.
4. There is a sudden change in volume when it melts. 4. There is no sudden change in volume on melting.

5. Crystalline solids have well-defined cleavage planes. 5. Amorphous solids cleavage into uneven parts with
ragged edges.
6. They are anisotropic because of these crystalline substances 6. They are isotropic because of these amorphous
show different property in different direction. substances show same property in all directions.
7. Crystalline solids exhibit an X-ray diffraction pattern. 7. They do not give any X-ray diffraction pattern.
Why Crystalline solids are anisotropic?
Crystal Lattice

 The regular array of points, which defines

the position of atoms, molecules or ions
in a crystal, is called crystal lattice.
 Each point must have the same number of Lattice points (may be atoms,
molecules or ions)
neighbors as every other point and the
neighbors must always be found at the
same distances and directions.
 All points are in the same environment.
Crystal Lattice

Lattice point: The point that describes the position of an atom,

molecule, or ion in a crystal is called a lattice point.

Motif: A motif is a unit of pattern. In a crystal, it is an atom, a

molecule, an ion or a group of atoms, molecules or ions.

Lattice + Motif Crystal

Unit Cell
 The smallest repeating unit of a crystal lattice is called a unit cell.
 It contains an integer number of lattice points.
 A unit cell has one lattice point at each corner, and there may be
lattice points in the faces, and in the interior of the cell as well.
Z
c

Unit cell  b

Y

a
X Unit cell
 Z
Unit Cell c

 The unit cell is characterized by six parameters, three axial


lengths and three interaxial angles. The lengths of the unit  b
Y

cell edges are designated a, b, c, and the interaxial angles α, β, a
γ. The angle α is between b and c, β is between c and a, while X Unit cell
γ is between a and b.
 The entire crystal consists of a large number of unit cells
adjacent to one another in all three dimensions. The unit cell
of a crystal possesses all the structural properties of the
given crystal.
 The unit cell can be described as a parallelepiped defined by
the cell edges a, b, and c, which are vectors. Its volume can be
calculated by the scalar triple product, V = (a · b × c, where a,
b, and c are the lattice vectors) and corresponds to the square
root of the determinant of the metric tensor.
Crystal System
 The crystal system is a grouping of crystal structures that are categorized according to the
axial system used to describe their lattice.
 Each crystal system consists of a set of three axes in a particular geometrical arrangement.
The seven unique crystal systems are:

(i) Triclinic (ii) Monoclinic

a ≠ b ≠ c, a ≠ b ≠ c,
α ≠ β ≠ γ ≠ 90o α = γ = 90o, β > 90o
K2Cr2O7, H3BO3 NaHCO3, S
Crystal System

(iii) Orthorhombic (iv) Tetragonal

a ≠ b ≠ c, a = b ≠ c,
α = β = γ = 90o α = β = γ = 90o
KNO3, BaSO4 SnO2, TiO2
Crystal System

(v) Cubic (vi) Hexagonal

a = b = c, a = b ≠ c,
α = β = γ = 90o α = β = 90o, γ =120o
NaCl, KCl SiO2, ZnO
Crystal System

(vii) Rhombohedral
a = b = c,
α = β = γ ≠ 90o
CaSO4, KMnO4
 Acknowledgement

Dr. Pradip Kumar Bakshi

Former Professor, Department of Chemistry
University of Dhaka
5. Write the difference between crystalline and amorphous
solids. (2)
6. Why are crystalline solids anisotropic? (3)
7. Write the names of the seven crystal systems with
mentioning the lengths of the edges and angles between
them. (3)
8. Why can a spider not walk on a surface of ethanol, even if
it can walk on water? (2)
Thanks